Flowable composition and a process for making the flowable composition

ABSTRACT

The invention concerns the preparation of azlactone-derivatized polyamides which are obtained by reacting polyamides with a solution containing an azabicyclo compound and a vinyl azalactone derivative of formula (I), in which R 1 , R 2  and R 3 , independently of one another, designate H or CH 3 ; and R 4  and R 5 , independently of each other, designate H or C 1  to C 5  alkyl. These azlactone-derivatized polyamides can be used to bond amino-group-containing compounds to a matrix. Examples of these polyamides include affinity carriers and immobilized enzymes.

FIELD OF THE INVENTION

[0001] This invention relates to a flowable nondigestible oilcomposition containing a solid nondigestible oil component, which canflow at ordinary and ambient storage temperatures, and to a process formaking the flowable nondigestible oil.

BACKGROUND ART

[0002] Numerous patents have been directed to providing materials whichhave the physical and gustatory characteristics of triglyceride fats,but which are absorbed to a low extent or not at all by the body. Thesematerials are referred to variously as noncaloric fats, pseudofats,nondigestible fats and fat substitutes. Patents pertaining to suchmaterials include U.S. Pat. Nos. 4,582,927, Fulcher, issued Apr. 15,1986, (fatty esters of malonic acid); 4,582,715, Volpenhein, issued Apr.15, 1986, (alpha acetylated triglycerides); and 3,579,548, Whyte, issuedMay 18, 1981, (triglycerides of alpha-branched chain carboxylic acids).

[0003] One particular type of compound which has achieved considerableattention as a nondigestible fat is sucrose polyester (i.e., sucrose inwhich at least four of the eight hydroxyl groups are esterified with afatty acid). U.S. Pat. Nos. 3,600,186, Mattson, issued Aug. 17, 1971;4,368,213, Hollenbach et al. issued Jan. 11, 1983; and 4,461,782,Robbins et al. issued Jul. 24, 1984 describe the use of this material asa nondigestible fat in a variety of food compositions.

[0004] A problem associated with use of liquid nondigestible oils, i.e.,those having a melting point below body temperature (about 37° C.), isan undesired passive oil loss effect, which is manifested in leakage ofthe liquid nondigested fat through the gastrointestinal tract's analsphincter. Regular ingestion of moderate to high levels of completelyliquid forms of these polyol polyesters can produce this passive oilloss. U.S. Pat. No. 4,005,195, Jandacek, issued Jan. 25, 1977, disclosesthe combining of higher melting fatty materials such as solidtriglycerides and solid sucrose polyesters with the liquid sucrosepolyesters in order to control oil loss.

[0005] U.S. Pat. 4,797,300 (Jandacek et al.), issued Jan. 10, 1989discloses the use of certain solid sucrose polyesters which have highoil binding capacity for liquid sucrose polyesters (SPE) and liquidtriglycerides, when used at levels of about 10% to 25% in said oils. Itis disclosed that because of their high oil binding capacity, thesesolid sucrose polyesters have outstanding utility as agents to preventpassive oil loss of liquid nondigestible sucrose polyesters, and theyare also useful as noncaloric hardstocks to use with liquid digestibleor nondigestible oils in the preparation of semisolid fat products suchas shortenings and margarines. The oil binding agents of the Jandacek etal. '300 patent are solid sucrose polyesters wherein the ester groupsconsist essentially of a mixture of short chain saturated fatty acidester radicals (C₂-C₁₀) and long chain saturated fatty acid radicals(C₂₀-C₂₄) in a molar ratio of short chain to long chain of from about3:5 to about 5:3, and wherein the degree of esterification is from about7 to about 8. Jandacek et al. also disclose plastic shortening and otherfood compositions containing 10-25% of the solid SPE.

[0006] U.S. Pat. No. 4,005,195 (Jandacek), issued Jan. 25, 1977describes a means of preventing the undesirable oil loss effect throughthe addition of the polyesters as oil-loss control agents. The oil-losscontrol agents include solid fatty acids (melting point 37° C. orhigher) and their triglyceride sources, and solid polyol fatty acidpolyesters. Specifically C₁₀-C₂₂ saturated fatty acid polyesters aresaid to be useful at levels of at least 10%, preferably at least 20%.

[0007] U.S. Pat. No. 5,306,514 (Letton et al.), issued Apr. 26, 1994,discloses edible oil compositions containing a) a liquid nondigestibleoil having a complete melting point below about 37° C., and b) a solidpolyol fatty acid polyester having a complete melting point above about37° C., wherein the weight ratio of b) to a) is from about 1:99 to about9:91. The solid polyol fatty acid polyester consists of (i) a polyolhaving at least about 4 hydroxyl groups, wherein at least about 4 of thehydroxyl groups of the polyol are esterified, and (ii) ester groupscomprised of (a) fatty acid radicals selected from the group consistingof C₁₂ or higher unsaturated fatty acid radicals, C₂-C₁₂ saturated fattyacid radicals, or mixtures thereof, and (b) C₂₀ or higher saturatedfatty acid radicals, at a molar ratio of (a):(b) being from about 1:15to about 1:1. In the solid polyol polyester at least 15% by weight ofthe fatty acid radicals C₂₀ or higher saturated fatty acid radicals.Further, the slope of the SFC profile of the mixture of a) and b)between 37° C. and 21.1° C. is between 0 and about −0.75.

[0008] U.S. Pat. 5,306,515 (Letton et al.), issued Apr. 26, 1994,discloses pourable compositions containing a solid polyol fatty acidpolyester, having a complete melting point above about 37° C., a liquidnondigestible oil having a complete melting point below about 37° C.,less than about 90% by weight of a digestible oil having less than 5%solids at 21° C.; and less than 10% hardstock; wherein the ratio of (A)to (B) is from about 1:99 to about 9:91 and wherein the pourablecomposition has a yield point of not more than about 100 dynes/cm². Thesolid polyol fatty acid polyester consists of (i) a polyol having atleast about 4 hydroxyl groups, wherein at least about 4 of the hydroxylgroups of the polyol are esterified, and (ii) ester groups comprised of(a) fatty acid radicals selected from the group consisting of C₁₂ orhigher unsaturated fatty acid radicals, C₂-C₁₂ saturated fatty acidradicals or mixtures thereof, and (b) C₂₀ or higher saturated fatty acidradicals at a molar ratio of (a):(b) being from about 1:15 to about 2:1.In the solid polyol polyester at least 15% by weight of the fatty acidradicals are C₂₀ or higher saturated fatty acid radicals. Further, theslope of the SFC profile of the mixture of (A) and (B) between 37° C.and 21.1° C. is between 0 and about −0.75, and the combined level of (A)and (B) in said composition is at least 10% by weight. Examples includecompositions containing 65 wt. % liquid digestible triglyceride oil.

[0009] Additionally, the following patent documents provide descriptionrelated to esterified propoxylated glycerins, esterified linkedalkoxylated glycerins, and/or esterified epoxide extended polyols: U.S.Pat. Nos. 4,861,613 to Pollard; 4,983,329 to Cooper; 5,175,323 toCooper; 5,273,772 to Cooper; 5,304,665 to Cooper; 5,399,728 to Cooper;5,512,213 to Cooper; 5,603,978 to White; 5,641,534 to White; EPO PatentDocuments 325,010 published Jul. 26, 1989 in the name of White et al.;667,105 published Aug. 16, 1995 in the name of Ziegert et al.; PCTPublication WO 97/222260; U.S. Pat. Nos. 5,273,772 to Cooper; 5,362,894to Handweker; 5,374,446 to Ferenz; 5,427,815 to Ferenz; 5,516,544 toSekula; EPO Patent Document 571,219 published Nov. 24, 1993 in the nameof Masten.

SUMMARY OF THE INVENTION

[0010] It is an object of the present invention to provide a flowablenondigestible oil composition containing a solid component at ambienttemperature, which flowable oil composition is flowable at ordinary andambient temperatures, and which flowable oil composition cansubsequently be used as an edible nondigestible or partially digestibleoil providing good passive oil loss control and good organolepticproperties to foods prepared with them.

[0011] According to one aspect of the present invention, a flowablenondigestible composition, such as a flowable nondigestible oilcomposition, is provided. The flowable composition comprises a liquidcomponent having a complete melt point less than 37° C. and a solidcomponent having a complete melt point of at least about 37° C., whereinthe solid component is in the form of crystallized particles. One orboth of the liquid and solid components comprises a material selectedfrom esterified linked alkoxylated polyols, such as esterified linkedalkoxylated glycerines; esterified epoxide-extended polyols; andmixtures thereof.

[0012] In one embodiment, the solid component comprises a materialselected from esterified linked alkoxylated polyols, such as esterifiedlinked alkoxylated glycerines; esterified epoxide-extended polyols; andmixtures thereof; and the liquid component comprises a liquidnon-alyoxylated polyol fatty acid polyester such as a liquid sucrosepolyester.

[0013] In another embodiment, the solid component comprises a solidnon-alkoxylated polyol fatty acid polyester, such as a sucrosepolyester, and the liquid component comprises a material selected fromesterified linked alkoxylated polyols, such as esterified linkedalkoxylated glycerines; esterified epoxide-extended polyols; andmixtures thereof.

[0014] In yet another embodiment, solid component comprises a materialselected from esterified linked alkoxylated polyols, such as esterifiedlinked alkoxylated glycerines; esterified epoxide-extended polyols; andmixtures thereof; and the liquid component comprises a material selectedfrom liquid esterified linked alkoxylated polyols, such as esterifiedlinked alkoxylated glycerines; esterified epoxide-extended polyols; andmixtures thereof.

[0015] The flowable composition has a Consistency (K) within thetemperature range of 20-40° C. of less than about 600 P.sec^((n−1)),where K is determined from a power law model fit of the apparentviscosity versus shear rate data (see Analytical Method Section), and nis the shear index (dimensionless). In one embodiment, the compositioncan have a Consistency of less than about 400, more particularly lessthan about 200, and still more particularly less than about 100P.sec^((n−1)) in a temperature range of 20-40 degrees Centigrade.

[0016] The flowable composition can contain the solid component in theform of small crystal particles, typically having a largest dimension ofless than about 30 microns, preferably less than about 10 microns, morepreferably between 1 and 30 microns, even more preferably between 1 and10 microns, and most preferably of about 2 to about 5 microns.

[0017] The present invention also provides a process for making aflowable nondigestible oil composition comprising a liquid componenthaving a complete melt point less than 37° C., and a solid componenthaving a complete melt point of at least about 37° C.. The processcomprises the steps of:

[0018] a) providing a mixture comprising the liquid component and thesolid component, wherein at least one of the liquid component and thesolid component comprises a material selected from esterified linkedalkoxylated polyols, such as esterified linked alkoxylated glycerines;esterified epoxide-extended polyols; and mixtures thereof;

[0019] b) melting the mixture of the liquid component and the solidcomponent;

[0020] c) crystallizing at least a substantial portion of the solidcomponent; and

[0021] d) shearing the mixture of the liquid component and the solidcomponent during the step of crystallizing, thereby forming at least asubstantial portion of the solid component into crystallized particles.

[0022] According to one embodiment, the process comprises the steps ofmelting completely the mixture containing the solid component, rapidlycooling the melted mixture to a crystallization temperature, therebyrapidly crystallizing at least a substantial portion of the solidcomponent, and shearing the mixture during the step of crystallizing toform the flowable nondigestible oil composition. Optionally, followingthe crystallizing and shearing steps, the process can include one orboth of the following steps: 1) the step of tempering the crystallizednondigestible oil composition for a time sufficient to substantiallycompletely crystallize all of the solid component, and/or 2) the step ofadding a stabilizing amount of a diluent liquid, typically a liquidpolyol fatty acid polyester, to the crystallized nondigestible oilcomposition, or both steps.

[0023] These compositions are capable of being stored in a flowablestate at ambient and ordinary storage temperatures. Storage at ambientand ordinary temperature avoids exposure of the composition to hightemperatures (generally greater than 50° C.) usually associated withstorage and handling of the nondigestible oil composition in a moltenform. Making and storing the nondigestible oil in a flowable form allowsthe nondigestible oil to be easily handled at ambient handling andstorage temperatures, which minimizes the effect of heat and hightemperature on the chemical stability of the polyol fatty acidpolyester. This results in greater oxidative and flavor stability duringextended storage of the nondigestible oil and of food productscontaining the nondigestible oil. This is particularly advantageous whenthe liquid component of the nondigestible oil is made from an unhardened(non-hydrogenated) source oil, such as unhardened cottonseed oil. Inaddition, the flowable nondigestible oil of the present invention can beutilized as a carrier for the application or incorporation ofingredients to foods products, such as flavorings, seasonings, andvitamins.

[0024] Without being limited by theory, it is believed that the use ofesterified linked alkoxylated polyols, such as esterified linkedalkoxylated glycerines; esterified epoxide-extended polyols; andmixtures thereof, provide the advantage that the flowable compositionhaving such materials are less likely to be associated withgastro-intestinal symptoms than are flowable compositions which do notinclude such materials.

BRIEF DESCRIPTION OF THE DRAWINGS

[0025]FIGS. 1a through 1 c depict sucrose octaester monomer, dimer andtrimer, respectively.

DEFINITIONS

[0026] As used herein the term “nondigestible” shall mean beingabsorbable to an extent of only 70% or less (especially 40% or less,more particularly 20% or less) by the human body through its digestivesystem.

[0027] As used herein, the term “flowable” refers to ability of acomposition to be transported by gravity or by conventional mechanicalor pneumatic pumping means from a storage vessel.

[0028] As used herein the term “ambient” shall mean a temperature whichis less than the lowest onset crystallization temperature of a solidpolyol fatty acid polyester in the nondigestible oil composition.

[0029] As used herein, the term “food” refers to any manner of viand forusage by man. “Food” may further include individual food components ormixtures thereof.

[0030] As used herein, the term “comprising” means various componentscan be conjointly employed in the fat compositions of the presentinvention. Accordingly, the term “comprising” encompasses the morerestrictive terms “consisting essentially of” and “consisting of”.

[0031] All percentages and proportions herein are by weight unlessotherwise specified.

DETAILED DESCRIPTION OF THE INVENTION

[0032] High temperatures and exposure to oxygen can result in thermaland oxidative decomposition of the nondigestible oil composition. It ispreferred to avoid storage and handling of the nondigestible oil at thehigher temperatures provided in heated railway cars and productiontanks, which are needed to maintain the nondigestible oil in a moltenstate.

[0033] Consequently, there is a significant advantage to store andtransport the nondigestible oil at lower, ambient temperatures, and inthe absence of oxygen, to inhibit or reduce thermal and oxidativedegradation of the nondigestible oil composition, to improve the qualityof the nondigestible oil composition and the foods prepared therewith,and to require less expensive and less complicated transportation andstorage requirements for the nondigestible oil composition. Generally,the ambient temperature at which the flowable nondigestible oil of thepresent invention would be stored is from about 5° C. to about 50° C.,and more preferably from about 20° C. to about 40° C.

[0034] To commercially process the nondigestible oil economically and inlarge quantities, there is a need for a rapid process to make a flowablenondigestible oil composition which can be handled and stored at ambienttemperature. Such a process would convert the nondigestible oil into aflowable nondigestible oil at ambient conditions in less than 2 hours,preferably in less than one hour, and more preferably in less than 30minutes. For commercial reasons, the flowable nondigestible oilcomposition of the present invention should have good flow properties,such that the flowable nondigestible oil will drain sufficiently,preferably substantially completely, by the force of gravity from theinside of transportation vessels, such as railway cars, andmanufacturing containers, such as tanks. Preferably, the flowablenondigestible oil composition of the present invention generally willnot adhere in a mass to the side walls and other surfaces inside therailway cars or tanks. That is, the flowable nondigestible oil willtypically drain such that only a relatively thin layer or film of thenondigestible oil will remain on the inside surfaces of a vessel ortank. Preferably, the flowable nondigestible oil is stable duringextended storage; that is, it remains flowable and there is minimal andpreferably no separation or settling of the solid crystals.

[0035] I. Composition of Flowable Nondigestible Oil

[0036] A flowable nondigestible oil composition comprising a solidcomponent having a complete melting point of at least about 37° C. and aliquid component having a complete melting point of less than about 37°C., can be prepared which is flowable at ambient storage temperatures,and can, upon further processing including remelting completely thesolid component, provide good passive oil loss control and organolepticproperties (i.e. good mouthfeel) to foods prepared therewith.

[0037] The flowable nondigestible oil composition of the presentinvention generally comprises about 50% to about 99%, more preferablyabout 80% to about 97%, and most preferably about 85% to about 95%, ofthe liquid component. In one embodiment, the solid component comprises asolid sucrose polyester, and the flowable nondigestible oil compositioncomprises about 1% to about 50%, more preferably about 3% to about 20%,and most preferably about 5% to 15%, of the solid sucrose polyester. Inanother embodiment, the solid component comprises a material selectedfrom esterified linked alkoxylated polyols, esterified epoxide extendedpolyols, and mixtures thereof; and the flowable nondigestible oilcomposition comprises about 1% to about 50%, more preferably about 5% toabout 30%, of the solid component.

[0038] The flowable nondigestible oil composition generally has aConsistency of less than 600 P.sec^((n−1)) in a temperature range offrom 20-40° C. The flowable nondigestible oil composition can have aConsistency of preferably less than about 400 P.sec^((n−1)), moreparticularly less than about 200 P.sec^((n−1)), and still moreparticularly less than about 100 P.sec^((n−1)), in a temperature rangeof 20-40° C.

[0039] The compositions according to the present invention are furthercharacterized in having a relatively flat solids content profile acrossthe temperature range of from typical room temperature to bodytemperature, i.e., from about 21.1° C. (70° F.) to about 37° C. (98.6°F.). The slope of the SFC profile is expressed as the change in percentsolids per unit change in temperature, in ° F. Typically the slope ofthe Solid Fat Content (SFC) profile between these temperatures isbetween 0 and −0.75. More particularly, the slope can be between 0 and−0.5, and still more particularly between 0 and −0.3.

[0040] Generally, where the solid component comprises C20 or highersaturated fatty acid radicals, the higher the weight percent of C₂₀ orhigher saturated fatty acid radicals in the solid polyol polyester, theflatter the SFC profile slope will be. For example, if the solidcomponent comprises solid polyol polyester containing C20 or highersaturated fatty acid radicals, then at the 30% C₂₀ or higher fatty acidlevel the slope can be between 0 and −0.5, and at 50% it will typicallybe between 0 and −0.3.

[0041] Determination of SFC values over a range of temperatures can bedone by a method involving PNMR (Pulsed Nuclear Magnetic Resonance).Such method is well known to those skilled in the art (see J. Amer. OilChem. Soc., Vol. 55 (1978), pp. 328-31, and A.O.C.S. Official Method Cd.16-81, Official Methods and Recommended Practices of The American OilChemists Society, 3rd. Ed., 1987; both incorporated herein byreference).

[0042] In one embodiment, the solid component comprises a materialselected from esterified linked alkoxylated polyols, such as esterifiedlinked alkoxylated glycerines; esterified epoxide-extended polyols; andmixtures thereof; and the liquid component comprises a liquidnon-alkoxylated polyol fatty acid polyester such as a liquid sucrosepolyester.

[0043] In another embodiment, the solid component comprises a solidnon-alkoxylated polyol fatty acid polyester, such as a sucrosepolyester, and the liquid component comprises a material selected fromesterified linked alkoxylated polyols, such as esterified linkedalkoxylated glycerines; esterified epoxide-extended polyols; andmixtures thereof

[0044] In yet another embodiment, solid component comprises a materialselected from esterified linked alkoxylated polyols, such as esterifiedlinked alkoxylated glycerines; esterified epoxide-extended polyols; andmixtures thereof; and the liquid component comprises a material selectedfrom liquid esterified linked alkoxylated polyols, such as esterifiedlinked alkoxylated glycerines; esterified epoxide-extended polyols; andmixtures thereof.

[0045] Suitable alkoxylated polyols include alkoxylated glycerol,alkoxylated polyglycerols, sorbitol alkoxylated glycerins, alkoxylatedpolysaccharides, and linked alkoxylated polyols such as linkedalkoxylated glycerins. Polyols may be alkoxylated with C₃-C₆ epoxides,such as propylene oxide, butylene oxide, isobutylene oxide, and penteneoxide, to produce epoxide-extended polyols having an epoxylation indexminimum of at least about 2, preferably in the range of from about 2 toabout 8, as described in U.S. Pat. No. 4,816,613, incorporated herein byreference. Polyols may be also alkoxylated with an epoxide, preferably aC₃-C₁₀ 1,2alkylene oxide, in the presence of a ring-openingpolymerization catalyst, as described in U.S. Pat. Nos. 5,399,729 and5,512,313, incorporated herein by reference.

[0046] Suitable alkoxylated polyols are also described in U.S. Pat. Nos.4,983,329; 5,175,323; 5,288,884; 5,298,637; 5,362,894; 5,387,429;5,446,843; 5,589,217; 5,597,605; 5,603,978 and 5,641,534, allincorporated herein by reference. Suitable alkoxylated polyols includealkoxylated sugar alcohols, alkoxylated monosaccharides, alkoxylateddisaccharides, alkoxylated polysaccharides, alkoxylated C₂-C₁₀ aliphaticdiols, and alkoxylated C₃-C₁₂ aliphatic triols. Preferred alkoxylatedC₃-C₁₂ aliphatic triols are alkoxylated glycerols, more preferred arepropoxylated glycerols, and particularly preferred are propoxylatedglycerols having from about 3 to about 21 moles of propylene oxide permole glycerol. Preferred alkoxylated polysaccharides are alkoxylatedpolysaccharides containing anhydromonosaccharide units, more preferredare propoxylated polysaccharides containing anhydromonosaccharide units,as described in U.S. Pat. No. 5,273,772, incorporated herein byreference. Suitable linked alkoxylated glycerins include thosecomprising polyether glycol linking segments, as described in U.S. Pat.No. 5,374,446, incorporated herein by reference, and those comprisingpolycarboxylate linking segments, as described in U.S. Pat. Nos.5,427,815 and 5,516,544, incorporated herein by reference; morepreferred are those described in U.S. Pat. No. 5,516,544.

[0047] As used herein, the term “polyol fatty acid polyesters” isintended to include fatty acid esters of polyols, in which the hydroxylgroups are replaced with esters of fatty acids. Suitable fatty acidesters can be derived from either saturated or unsaturated fatty acids.Suitable preferred fatty acids include, for example, capric, lauric,palmitic, stearic, behenic, isomyristic, isomargaric, myristic,caprylic, and anteisoarachadic. Suitable preferred unsaturated fattyacids include, for example, maleic, linoleic, licanic, oleic, elaidic,linolenic, erythrogenic acids. In a preferred embodiment of theinvention the fatty acid chains of the esterified polyols have fromabout two to about twenty-four carbon atoms. Polyol fatty acidpolyesters obtained from naturally occurring oil such as soybean oil,cottonseed oil, palm kernel oil, palm oil, coconut oil, sunflower oil,safflower oil, rapeseed oil, high erucic acid rapeseed oil, canola oil,tallow oil, peanut oil and corn oil are preferred. The oils can be fullyhydrogenated or partially hydrogenated oils.

[0048] Suitable polyol fatty acid polyesters are esterified linkedalkoxylated glycerins, including those comprising polyether glycollinking segments, as described in U.S. Pat. No. 5,374,446, incorporatedherein by reference, and those comprising polycarboxylate linkingsegments, as described in U.S. Pat. Nos. 5,427,815 and 5,516,544,incorporated herein by reference; more preferred are those described inU.S. Pat. No. 5,516,544.

[0049] Additional suitable polyol fatty acid polyesters are esterifiedepoxide-extended polyols of the general formula P(OH)_(A+C) (EPO)_(N)(FE)_(B) wherein P(OH) is a polyol, A is from 2 to about 8 primaryhydroxyls, C is from about 0 to about 8 total secondary and tertiaryhydroxyls, A+C is from about 3 to about 8, EPO is a C₃-C₆ epoxide, N isa minimum epoxylation index average number, FE is a fatty acid acylmoiety and B is an average number is the range of greater than 2 and nogreater than A+C, as described in U.S. Pat. No. 4,861,613 and EP 0324010Al, incorporated herein by reference. The minimum epoxylation indexaverage number has a value generally equal to or greater than A and is anumber sufficient so that greater than 95% of the primary hydroxyls ofthe polyol are converted to secondary or tertiary hydroxyls. Preferablythe fatty acid acyl moiety has a C₇-C₂₃ alkyl chain.

[0050] Suitable esterified epoxide-extended polyols include esterifiedpropoxylated glycerols prepared by reacting a propoxylated glycerolhaving from 2 to 100 oxypropylene units per glycerol with C₁₀-C₂₄ fattyacids or with C₁₀-C₂₄ fatty acid esters, as described in U.S. Pat. Nos.4,983,329 and 5,175,323, respectively, both incorporated herein byreference. Also suitable are esterified propoxylated glycerols preparedby reacting an epoxide and a triglyceride with an aliphatic polyalcohol,as described in U.S. Pat. No. 5,304,665, incorporated herein byreference, or with an alkali metal or alkaline earth salt of analiphatic alcohol, as described in U.S. Pat. No. 5,399,728, incorporatedherein by reference. Also suitable are acylated propylene oxide extendedglycerols having a propoxylation index of above about 2, preferably inthe range of from about 2 to about 8, more preferably about 5 or above,wherein the acyl groups are C₈-C₂₄, preferably C₁₄-C₁₈, compounds, asdescribed in U.S. Pat. Nos. 5,603,978 and 5,641,534, both incorporatedherein by reference.

[0051] Other suitable esterified epoxide-extended polyols includeesterified alkoxylated polysaccharides. Suitable esterified alkoxylatedpolysaccharides are esterified alkoxylated polysaccharides containinganhydromonosaccharide units, more preferred are esterified propoxylatedpolysaccharides containing anhydromonosaccharide units, as described inU.S. Pat. No. 5,273,772, incorporated herein by reference

[0052] A. Solid Component

[0053] 1. Esterified Linked alkoxylated glycerins/Esterifiedepoxide-extended polyols

[0054] The polyol fatty acid polyester of the solid component of thepresent invention will have a complete melt point of at least 37° C.,which is the ordinary body temperature, and more preferably of at least50° C., and most preferably of at least 60° C., and less than 500° C.

[0055] Suitable polyol fatty acid polyesters of the solid componentcomprise saturated fatty acid esters having a chain length of at least16 (C16 or greater), and diversely esterified polyol polyesters havinglong chain unsaturated fatty acid radicals and short chain fatty acidradicals, as described hereinafter under “Solid Diversely EsterifiedPolyol Polyesters.” In one embodiment, the solid component used to formthe flowable nondigestible oil compositions of the present invention canbe a solid component comprising a polyol fatty acid polyester selectedfrom esterified linked alkoxylated polyols, such as esterified linkedalkoxylated glycerines; esterified epoxide-extended polyols; andmixtures thereof.

[0056] The following patent documents are incorporated herein byreference and disclose esterified linked alkoxylated polyols and/oresterified epoxide-extended polyols which are suitable for use as thesolid component: U.S. Pat. Nos. 5,273,772 to Cooper; 5,362,894 toHandweker; 5,374,446 to Ferenz; 5,427,815 to Ferenz, 5,516,544 toSekula; EPO Patent Document 571,219 published Nov. 24, 1993 in the nameof Masten

[0057] 2. Other Solid Polyol Fatty Acid Polyester

[0058] As described above, the solid polyol fatty acid polyester of thepresent invention will have a complete melt point of at least 37° C.,which is the ordinary body temperature, and more preferably of at least50° C., and most preferably of at least 60° C., and less than 500° C. Inan alternative embodiment, the solid component comprises a solidnon-alkoxylated polyol fatty acid polyester selected from (i) a solidsaturated polyol polyester, (ii) a solid diversely esterified polyolpolyester, (iii) a polyol polyester polymer, and (iv) combinationsthereof.

[0059] Such polyols which are used in the solid component of suchalternative embodiments of the present invention preferably contain fromabout 4 to about 12, more preferably 4 to 8, most preferably 6 to 8,hydroxyl groups. Examples of preferred polyols are sugars (includingmonosaccharides and disaccharides and trisaccharides) and sugaralcohols, containing from 4 to 11 hydroxyl groups. The trisaccharidesraffinose and maltotriose are examples of sugars which contain 11hvdroxyl groups. The preferred sugars and sugar alcohols are those whichcontain 4 to 8, more preferably 6 to 8, hydroxyl groups. Examples ofthose containing four hydroxyl groups are the monosaccharides xylose andarabinose and the sugar alcohol erythritol. Suitable five hydroxylgroup-containing polyols are the monosaccharides galactose, fructose,mannose and glucose, and the sugar alcohol xylitol. A polyol containingsix hydroxyl groups is sorbitol. Examples of disaccharide polyols whichcan be used include maltose, lactose, and sucrose, all of which containeight hydroxyl groups. Examples of other suitable polyols arepentaerythritol, diglycerol, triglycerol, alkyl glycosides, andpolyvinyl alcohols. One preferred polyol is sucrose.

[0060] The average degree of esterification of the solid polyol fattyacid polyesters is of at least 4 ester groups, i.e., at least 4 of thehydroxyl groups of the polyol are esterified with fatty or other organicacids. Polyol esters that contain 3 or less ester groups are generallydigested in (and the products of digestion are absorbed from) theintestinal tract much in the manner of ordinary triglyceride fats oroils, whereas those polyol esters which contain 4 or more ester groupsare generally substantially nondigestible and consequently nonabsorbableby the human body. It is not necessary that all of the hydroxyl groupsof the polyol be esterified, but it is preferable that disaccharidemolecules contain no more than 3 unesterified hydroxyl groups, and morepreferably no more than 2 unesterified hydroxyl groups, so that they arerendered nondigestible. Typically, substantially all (e.g., at leastabout 85%) of the hydroxyl groups of the polyol are esterified,preferably at least about 95% of the hydroxyl groups of the polyol areesterified. In the case of sucrose polyesters, typically from about 7 to8 of the hydroxyl groups of the polyol are esterified.

[0061] In one embodiment, the solid polyol fatty acid polyestercomprises (i) a solid saturated polyol polyester, and (ii) a soliddiversely esterified polyol polyester, the ratio of (i):(ii) being fromabout 1:20 to about 4:1.

i) Solid Saturated Polyol Polyester

[0062] The solid saturated polyol polyester comprises esters ofessentially only, and preferably only, long chain saturated fatty acidradicals which are typically normal and contain at least 14, preferably14 to 26, and more preferably 16 to 24, and most preferably from 20 to24, carbon atoms. Particularly preferred are saturated fatty acidradicals of 22 carbon atoms. The long chained saturated radicals can beused in combination with each other in all proportions. The averagedegree of esterification of these solid saturated polyol polyesters issuch that at least 4 of the hydroxyl groups of the polyol areesterified. In the case of sucrose polysaturate esters, from about 7 to8 of the hydroxyl groups of the polyol are preferably esterified.Typically, substantially all (e.g., at least about 85%, preferably atleast about 95%/) of the hydroxyl groups of the polyol are esterified.

[0063] Examples of suitable long chain saturated fatty acid radicalsinclude tetradecanoate (myristate), hexadecanoate (palmitate),octadecanoate (stearate), eicosanoate (arachidate), docosanoate(behenate), tetracosanate (lignocerate), and hexacosanoate (cerotate).Mixed fatty acid radicals from completely or substantially completelyhydrogenated vegetable oils which contain substantial amounts of thedesired long chain saturated fatty acids can be used as sources of fattyacid radicals in preparing the solid polyol polyesters useful in thepresent invention. The mixed fatty acids from such oils shouldpreferably contain at least about 30% (more preferably at least about50%, most preferably at least about 80%) of the desired long chainsaturated fatty acids. Suitable source oils include completely orsubstantially completely hydrogenated soybean oil, cottonseed oil, palmoil, peanut oil, corn oil, safflower oil, sunflower oil, sesame oil, lowerucic acid rapeseed oil (i.e. canola oil), and high erucic acidrapeseed oil. These oils are typically hydrogenated to an Iodine Valueof about 12 or less, and preferably to an Iodine Value of about 8 orless.

[0064] Examples of solid polyol polyesters useful as hardstocks in thefat compositions of the present invention include sucrose octabehenate,sucrose octastearate, sucrose octapalmitate, sucrose heptastearate,xylitol pentastearate, galactose pentapalmitate, and the sucrose hepta-and octaesters of soybean oil and high erucic acid rapeseed oil fattyacids that have been hydrogenated to an Iodine Value of about 8 or less.

[0065] The solid saturated polyol polyester generally by itselfcrystallizes into well defined spherulitic particles from a moltencomposition at or below the onset crystallization temperature of thesolid saturated polyol polyester. The onset crystallization temperatureis that temperature at which a solid polyol fatty acid polyester canfirst begin to crystallize in the liquid polyol fatty acid polyester.That is, when dissolved in a molten composition comprising the solidsaturated polyol polyester in a liquid polyol fatty acid polyester, thesolid saturated polyol polyester will tend to form well defined, highlyordered, substantially sphere-shaped crystals, called spherulites, whenpermitted to cool and crystallize at a first crystallizationtemperature. In the absence of other solid nondigestible oil components,such as a solid diversely esterified polyol polyester or a polyolpolyester polymer, the solid saturated polyol polyester would normallycrystallize into spherical-shaped particles called spherulites having adiameter (or maximum particle dimension) of about 3 microns or larger,usually about 3-32 microns, the size being a function of the initialconcentration of the solid saturated polyol polyester in the liquidpolyol fatty acid polyester and the rate of shearing applied during thecrystallization. As will be understood from the processing descriptionherein after, if rapidly cooled and crystallized under shear, a solidsaturated polyol polyester will tend to crystallize as discretenonspherulite particles, typically of less than about 30 microns,preferably less than about 10 microns (although portion of the crystalscan form as very small spherulites may also form), as opposed to theabove mentioned larger shperulites which readily form at slower rates ofcooling (crystallizing) and slower rates of shear.

[0066] When cocrystallized with other solid polyol fatty acid polyestercomponents, such as the solid diversely esterified polyol polyesters orpolyol polyester polymers, the solid saturated polyol polyester willtend not to form the highly ordered spherulite particles.

[0067] In one embodiment, the flowable nondigestible compositioncomprises a solid component comprising solid saturated polyol polyesterssuch as sucrose polyol polyesters, and a liquid component comprising amaterial selected from esterified linked alkoxylated polyols, such asesterified linked alkoxylated glycerines; esterified epoxide-extendedpolyols; and mixtures thereof.

ii) Solid Diversely Esterified Polyol Polyesters

[0068] Suitable solid diversely esterified polyol polyesters for use informing the solid component comprise those polyol polyesters which havetheir ester group-forming fatty acid radicals selected so that thepolyol backbone does not contain all of a single type of ester group.Generally, these polyol polyesters contain two basic types of estergroups. These are (a) ester groups formed from long chain saturatedfatty acid radicals, as herein above described, and (b) dissimilar estergroups formed from acid radicals which are “dissimilar” to the longchain saturated fatty acid radicals. When these “dissimilar” fatty acidand/or other organic acid radicals are esterified onto a polyol thatcontains or will contain long chain saturated fatty acid radicals, theywill introduce diverse esterification into the resulting polyolpolyester molecule, thereby altering the crystal structure as thesemolecules pack together during crystallization. This diverseesterification can be due to differences in length of the ester-formingacid radicals (e.g., short chain versus long chain), or other stericfactors, e.g. branched chain versus straight chain, unsaturated chainversus saturated chain, aromatic chain versus aliphatic chain, etc.Polyol polyesters containing these “long chain” and “dissimilar” estergroups are therefore herein called “solid diversely esterified polyolpolyesters”.

[0069] The solid diversely esterified polyol polyesters tend to have“asymmetrical” or irregular molecular structures. It is believed thatthe asymmetrical structure of these molecules interfere with the normalpacking tendency of the symmetrical solid saturated polyol polyestermolecules during co-crystallization in the liquid polyol polyester. Thisinterference blocks the usual unrestrained three dimensional growth ofthe solid saturated polyol polyester molecules and thus inducesrestrained three dimensional growth or otherwise induces growth in, atmost two dimensions, e.g., the formation of relatively thinplatelet-like particles.

[0070] The dissimilar ester groups are formed from acid radicalsselected from long chain unsaturated fatty acid radical, short chainsaturated fatty acid radical, and other dissimilar fatty acid radicals,and mixtures thereof. The preferred dissimilar acid radical is a longchain unsaturated fatty acid radical.

[0071] The long chain unsaturated fatty acid radicals are typicallystraight chain (i.e., normal) mono- and di-unsaturates, and contain atleast about 12, preferably about 12 to about 26, more preferably about18 to 22, and most preferably 18 carbon atoms. Examples of suitable longchain unsaturated fatty acid radicals for the solid polyol polyestersherein are lauroleate, myristoleate, palmitoleate, oleate, elaidate,erucate, linoleate, linolenate, arachidonate, eicosapentaenoate, anddocosahexaenoate. For oxidative stability, the mono and/or diunsaturatedfatty acid radicals are preferred.

[0072] The short chain saturated fatty acid radicals are typicallynormal and contain 2 to 12, preferably 6 to 12 and most preferably 8 to12, carbon atoms. Examples of suitable short chain saturated fatty acidradicals are acetate, butyrate, hexanoate (caproate), octanoate(caprylate), decanoate (caprate), and dodecanoate (laurate).

[0073] Other dissimilar ester-forming radicals can include fatty-fattyacid radicals having at least one hydroxyl group that is esterified withanother fatty or other organic acid. Nonlimiting examples of suitablefatty-fatty acid radicals include 12-hydroxy-9-octadecenoic acid(ricinoleic acid), 12-hydroxy-octadecanoic acid, 9-hydroxy-octadecanoicacid, 9-hydroxy-10, 12-octadecadienoic acid, 9-hydroxy-octadecanoic, 9,10-dihydroxyoctadecanoic acid, 12, 12-dihydroxyeicosanoic acid, and18-hydroxy9, 11, 13-octadecatrienoic acid (kamolenic acid). Ricinoleicacid is a preferred hydroxy-fatty acid. Castor oil is a convenientsource of ricinoleic acid. Other sources of hydroxy-fatty acids includehydrogenated castor oil, strophanthus seed oils, calendula officinalisseed oils, hydrogenated strophanthus seed oils and hydrogenatedcalendula officinalis seed oils, cardamine impatiens seed oils, kanalaoils, mallotus discolor oils, and mallotus claoxyloides oils.

[0074] Specific, non-limiting examples of solid polyol fatty acidpolyesters of the present invention are sorbitol hexaester in which theacid ester radicals are palmitoleate and arachidate in a 1:2 molarratio; the octaester of raffinose in which the acid ester radicals arelinoleate and behenate in a 1:3 molar ratio; the heptaester of maltosewherein the esterifying acid radicals are sunflower seed oil fatty acidsand lignocerate in a 3:4 molar ratio; the octaester of sucrose whereinthe esterifying acid radicals are oleate and behenate in a 2:6 molarratio, and the octaester of sucrose wherein the esterifying acidradicals are laurate, linoleate and behenate in a 1:3:4 molar ratio. Apreferred material is sucrose polyester in which the degree ofesterification is 7-8, and in which the fatty acid radicals are C₁₈mono- and di-unsaturated and behenic, in a molar ratio of about 2:6 toabout 1.5:6.5.

[0075] In one embodiment, the flowable nondigestible compositioncomprises a solid component comprising solid diversely esterifiedsucrose polyol polyesters, and a liquid component comprising a materialselected from esterified linked alkoxylated polyols, such as esterifiedlinked alkoxylated glycerines; esterified epoxide-extended polyols; andmixtures thereof.

iii) Solid Polyol Polyester Polymers

[0076] Polyol polyester polymers are those formed by polymerizing apolyol polyester monomer to provide a molecule having at least twoseparate esterified polyol moieties linked by covalent bonds betweenester groups of these different polyol moieties. For example, twosucrose octabehenate monomers could be cross-linked between fatty acidsto form a polymer. Repeating units of such polyol polyester polymers canbe the same or different such that the generic term “polymer” in thiscontext includes the specific term “copolymer”. The number of repeatingmonomer (or co-monomer) units which make up such polyol polyesterpolymers can range from about 2 to 20, preferably from about 2 to 12.Depending on the method of preparing them, the polyol polyester polymersare frequently oligimers containing from 2 to 4 monomeric units, i.e.,are dimers, trimers, or tetramers. The most typical type of polyolpolyester polymer for use herein is dimer.

[0077] When sucrose is used as the polyol of the polyester polymer, itis preferably completely esterified with fatty acid or other estergroup-forming acid radicals. Using sucrose as the polyol, completelyesterified sucrose polyester monomer, dimer, and trimer are shownschematically in FIGS. 1a, 1 b, and 1 c, respectively. At least about15%, preferably at least about 45%, more preferably at least about 75%,and most preferably at least about 90% of the hydroxyl groups of thepolyol polyester polymer material should be esterified with long chain(C₂₀ and higher) saturated fatty acid radicals. The sucrose polyesterpolymers used herein can advantageously have a number average molecularweight of from about 4000 to about 60,000, preferably from about 4000 toabout 36,000, more preferably from about 5000 to about 12,000.

[0078] Suitable long chain saturated fatty acid radicals for use inpreparing the polyol polyester polymers (and its monomers) include thoseherein before described for preparing the solid diversely esterifiedpolyol polyesters. As in the case of the solid diversely esterifiedpolyol polyesters, mixed fatty acid radicals from source oils whichcontain substantial amounts of the desired long chain saturated fattyacids (i.e, at least about 30%, preferably at least about 50%, morepreferably at least about 80%) can be used as sources of acid radicalsin preparing these polyol polyester polymers.

[0079] Suitable polyol polyester material which forms the solidnondigestible particles used in the fat compositions herein willgenerally comprise from about 0% to 99% of the polyol polyester polymercomponent and from 1% to about 100% of the unpolymerized polyolpolyester monomer component, preferably from about 0% to about 90% ofthe polyol polyester polymer component and from about 10% to about 100%of the monomer component, more preferably from about 0% to 70% of thepolymer component and from 30% to about 100% of the monomer component,and most preferably from about 0% to 50% of the polymer component andfrom 50% to about 100% of the monomer component.

[0080] In one embodiment, the flowable nondigestible compositioncomprises a solid component comprising solid polyol polyester polymers,and a liquid component comprising a material selected from esterifiedlinked alkoxylated polyols, such as esterified linked alkoxylatedglycerines; esterified epoxide-extended polyols; and mixtures thereof.

iv. Processes for Making Solid Polyol Fatty Acid Polyesters

[0081] The solid polyol fatty acid polyesters, including the solidsaturated polyol polyester and the solid diversely esterified polyolpolyester, the solid polyol polyester polymer and the solid polyolpolyester polymer, used in the present invention can be made accordingto prior known methods for preparing polyesters of polyols. Since thesucrose polyesters are the preferred solid polyol polyesters herein, theinvention will be exemplified primarily by these materials.

[0082] One such method of preparation is by reacting the acid chloridesof the fatty acids with sucrose. In this method a mixture of the acidchloride or acid anhydrides of the fatty acids can be reacted in onestep with sucrose, or the acid chlorides can be reacted sequentiallywith sucrose. Another preparation method is by the process of reactingmethyl esters of the fatty acids with sucrose in the presence of a fattyacid soap and a basic catalyst such as potassium carbonate. See, forexample, U.S. Pat. Nos. 3,963,699, Rizzi et al., issued Jun. 15, 1976;4,518,772, Volpenhein, issued May 21, 1985; and 4,517,360, Volpenhein,issued May 14, 1985, and U.S. Ser. No. 417,990, Letton, filed Oct. 6,1989, all incorporated herein by reference. Methods for preparing polyolpolyester polymers are described in U.S. Pat. No. 5,451,416, issued Sep.19, 1995 (Johnston et. al.), the disclosure of which is incorporatedherein by reference.

[0083] When using the methyl ester route for preparing the solid polyolpolyesters herein, the fatty acid methyl esters are blended in thedesired ratio and reacted with sucrose by transesterification to obtainthe sucrose esters of mixed unsaturated/saturated or saturated fattyacids. In a preferred way of practicing the methyl ester process, fivemoles of the blended saturated/unsaturated or saturated methyl estersare reacted with sucrose in a first stage at 135° C. to obtain partialesters of sucrose. An additional nine moles of the blended esters arethen added and the reaction continued at 135° C. under reduced pressureuntil the desired degree of esterification has been attained.

[0084] When two or more of the solid saturated polyol polyester, soliddiversely esterified polyol polyester and solid polyol polyester polymerare used as the solid polyol polyester, then can be made andincorporated separately into the nondigestible oil composition, oralternatively, they can be made and mixed together and incorporated intothe nondigestible oil composition. In a preferred process where thesolid polyol fatty acid polyester comprises the solid saturated polyolpolyester and the solid diversely esterified polyol polyester, the twosolid polyesters are made simultaneously in the same polyolesterification preparation. The preferred method of making the solidpolyol fatty acid polyester is to esterify the polyol with a mixture oflong chain saturated fatty acid lower alkyl (preferably methyl) esters,and dissimilar fatty acid alkyl (preferably methyl) esters selected fromshort chain saturated fatty acid alkyl esters, long chain unsaturatedfatty acid alkyl esters, dissimilar acid alkyl esters, and mixturesthereof. When prepared in the same preparation, the esterification ofthe polyol hydroxy sites by the mixture of long chain saturated fattyacid radicals and dissimilar fatty acid radicals will occursubstantially randomly. In order to ensure that a portion of the solidpolyol polyesters are esterified only with long chain saturated fattyacid radicals, it is generally required to include proportionally moreof the long chain saturated fatty acid radicals as compared to thedissimilar fatty acid radicals. For example, sucrose has 8 hydroxy siteswhich are capable of being esterified. Depending upon the chain lengthsof the esters and other processing conditions, in order to obtain asignificant (10% or greater) amount of sucrose octasaturate and sucroseheptasaturate polyester from the reaction of sucrose with a mixture oflong chain saturated fatty acid methyl esters and long chain unsaturatedfatty acid methyl esters, a molar ratio of long chain saturated estersto long chain unsaturated esters of about 6:2 or more will be needed. Asan example of a particularly preferred solid polyol polyester, a molarratio of 6.5:1.5 of C22 saturated fatty acid ester to cottonseed oil(about 73% unsaturated) ester is used, resulting in about 20% on a molarbasis of sucrose octasaturate and sucrose heptasaturate polyester (asthe solid saturated polyol polyester), with the remaining polyesters(about 80% on a molar basis) being substantially octa- andhepta-substituted and having a mixture of long chain saturated fattyacid radicals and long chain unsaturated fatty acid radicals (as thediversely esterified polyol polyester). Increasing the ratio of longchain saturated radicals to long chain unsaturated radicals will resultin a higher proportion of the solid polyesters being converted to solidsaturated polyol polyesters; conversely decreasing the ratio of longchain saturated fatty acid radicals to long chain unsaturated fatty acidradicals will tend to result in a lower proportion of the solidpolyesters being converted to the solid saturated polyol polyesters.

[0085] Mixed fatty acid radicals from source oils which containsubstantial amount of the desired unsaturated or saturated acids can beused as the fatty acid radicals to prepare compounds of the invention.The mixed fatty acid radicals from the oils should contain at leastabout 30% (preferably at least about 50%, most preferably at least about80%) of the desired unsaturated or saturated acids. For example,rapeseed oil fatty acid radicals or soybean oil fatty acid radicals canbe used instead of pure C₁₂-C₂₆ unsaturated fatty acids. Hardened (i.e.,hydrogenated) high erucic rapeseed oil fatty acids can be used insteadof pure C₂₀-C₂₆ saturated fatty acids. Preferably the C₂₀ and higheracids (or their derivatives—e.g., methyl esters) are concentrated, forexample by distillation. The fatty acids from palm kernel oil or coconutoil can be used as a source of C₈ to C₁₂ acids. An example of the use ofsource oils to make solid polyol polyesters of the invention is thepreparation of solid sucrose polyester, employing the fatty acids ofhigh oleic sunflower oil and substantially completely hydrogenated higherucic rapeseed oil. When sucrose is substantially completely esterifiedwith a 1:3 by weight blend of the methyl esters of the fatty acids ofthese two oils, the resulting sucrose polyester will have a molar ratioof unsaturated C₁₈ acid radicals to C₂₀ and higher saturated acidradicals of about 1:1 and 28.6 weight percent of the total fatty acidsin the polyester will be C₂₀ and C₂₂ fatty acids. The higher theproportions of the desired unsaturated and saturated acids in the fattyacid stocks used in making the solid polyol polyester, the moreefficient the ester will be in its ability to bind liquid oils.

[0086] One way to prepare this material is by synthesizing monomericpolyol polyester according to known polyol esterification,transesterification and/or interesterification methods and by thenpolymerizing these monomers. The polymerization step can be initiatedand promoted by any of a number of well known methods, including, butnot limited to, photochemical reactions and reactions with transitionmetal ions, heat or free radical initiators such as di-tert-butylperoxide.

[0087] Alternatively, polyol polyester polymers can be prepared directlyby esterifying and/or interesterifying the polyol material withpolybasic polymerized fatty acids or their derivatives. For example, thepolyol polyester polymers could be prepared by reacting the acidchlorides or acid anhydrides of the desired esterifying polymer acidswith sucrose, preferably using a sequential esterification process inthe manner described herein before for the preparation of diverselyesterified polyol polyesters. The polyol polyester polymers could alsobe prepared by reacting the methyl esters of the desired polymer acidswith sucrose in the presence of a fatty acid soap and a basic catalystsuch as potassium carbonate in the manner described herein before forthe preparation of diversely esterified polyol polyesters.

[0088] When using the foregoing methods for preparing sucrose polyestermaterial containing both unpolymerized and polymerized fatty acidgroups, the molar ratio of unpolymerized to polymerized fatty acids inthe resulting sucrose material can range from about 2:6 to about 4:4.

[0089] When using the acid chloride or methyl ester procedures hereinbefore described to esterify the polyol with already polymerized fattyacids, a wide variety of prepolymerized fatty acid materials can beused. One such class of suitable polymerized fatty acids compriseslong-chain, aliphatic, dibasic acids having from about 28 to about 44carbon atoms in their molecules. They are generally formed fromunsaturated fatty acids having from about 14 to about 22 carbon atomswhich can be polymerized. For example linoleic acid can be polymerizedby heating to form linoleic acid dimer as follows:

[0090] Common examples of polymerizable acids of this type are thosecontaining two or more double bonds (polyunsaturated acids) such as theoctadecadienoic acids containing two double bonds, for example, theabove-mentioned linoleic acid, and the octadecatrienoic acids containing3 double bonds, for example, linolenic and eleostearic acids. Othercommon polymerizable polyunsaturated acids having from about 14 to about22 carbon which can be used to esterify polyols and thereby form thepolyol polyester polymers herein are octadecatrienoic acid (e.g.,licanic acid), actadectetraenoic acid (e.g., parinaric acid),eicosadienoic acid, eicostetraenoic acid (e.g., arachidonic acid),5,13-docosadienoic acid and clupanodonic acid. Monounsaturated fattyacids, such as oleic, elaidic and erucic acids, can also be used inpreparing suitable long chain fatty acid dimers which in turn can thenbe used to form the the solid polyol polyester polymer particles used inthe present invention.

[0091] Mixed fatty acid radicals from source oils which containsubstantial amounts of the desired polymerizable polyunsaturated ormonounsaturated fatty acids can be used as sources of acid radicals inpreparing the polyol polyester polymer materials used to form the solidparticles used in the present invention. The mixed fatty acids from suchsource oils should preferably contain at least about 30% (morepreferably at least about 50%, most preferably at least about 80%) ofthe desired polymerizable polyunsaturated or monounsaturated fattyacids.

[0092] Illustrative of natural sources which are rich in linoleic acidare soybean oil, cottonseed oil, peanut oil, corn oil, sesame seed oil,sunflower seed oil, safflower oil, linseed oil and perrilla oil.Oiticica oil is a particularly good source of licanic acid and tung oilcontains a high concentration of eleostearic acid. Fish oils, such asherring, menhaden, pilchard, salmon and sardine oil are also suitablesources of polymerizable acids, particularly the higher fatty acids suchas arachidonic and clupanodonic acids. Other oils such as tall oil,dehydrated castor oil, olive oil and rapeseed oil also containsignificant proportions of suitable unsaturated acids. For example,olive oil is rich in oleic acid and rapeseed oil is rich in erucic acid.

[0093] Preferred polybasic polymerized fatty acids and fatty acidderivatives for use in preparing polymer-containing polyol polyestersinclude dibasic acids produced by dimerization of the fatty acids orfatty acid lower esters derived from polyunsaturated vegetable oils suchas soybean oil or cottonseed oil or from animal fats such as tallow.

[0094] All of the foregoing types of polybasic polymerized fatty acidsmay themselves be made by a variety of methods known to those skilled inthe art. (See Lutton; U.S. Pat. No. 3,353,967; Issued Nov. 21, 1967,Goebel; U.S. Pat. No. 2,482,761; Issued Sep. 27, 1949, Harrison et al;U.S. Pat. No. 2,731,481; Issued Jan. 17, 1956 and Barrett et al; U.S.Pat. No. 2,793,219; Issued May 21, 1957, all of which are incorporatedherein by reference.) As noted, a mixture of both polymerized andunpolymerized polyol polyester material can be prepared by reacting thepolyol with both polymerized and unpolymerized esterifying fatty acidsor fatty acid derivatives. In a preferred method for preparingparticularly desirable solid sucrose polyester material comprisingsucrose polyester polymers, fractionated or unfractionated high erucicacid rapeseed (HEAR) methyl esters are partially polymerized, hardenedand then reacted with sucrose. Another method of making these especiallydesirable solid sucrose polyesters is to make liquid sucrose polyestermaterial esterified with fatty acid groups of high erucic acid rapeseedoil by a conventional process, to then partially polymerize theresulting liquid sucrose polyester material, and to then harden theresulting polymerized material.

[0095] B. Liquid Component:

[0096] The flowable nondigestible oil composition of the presentinvention also comprises a liquid component having a complete meltingpoint below about 37° C., which liquid component includes minimal or nosolids at body temperature (98.6 F., 37 C.).

[0097] 1. Liquid Esterified Linked alkoxylated glycerins/Esterifiedepoxide-extended polyols

[0098] In one embodiment, the liquid component used to form the flowablenondigestible oil compositions of the present invention can be a liquidcomponent comprising a material selected from esterified linkedalkoxylated polyols, such as esterified linked alkoxylated glycerines;esterified epoxide-extended polyols; and mixtures thereof.

[0099] The following patent documents are incorporated herein byreference and disclose esterified linked alkoxylated polyols and/oresterified epoxide-extended polyols which are suitable for use as theliquid component: U.S. Pat. Nos. 4,861,613 to Pollard; 4,983,329 toCooper; 5,175,323 to Cooper; 5,273,772 to Cooper; 5,304,665 to Cooper;5,399,728 to Cooper; 5,512,213 to Cooper; 5,603,978 to White; 5,641,534to White; EPO Patent Documents 325,010 published Jul. 26, 1989 in thename of White et al.; 667,105 published Aug. 16, 1995 in the name ofZiegert et al.; PCT Publication WO 97/222260.

[0100] 2. Other Liquid Polyol Fatty Acid Polyester

[0101] Other suitable liquid nondigestible edible oils for use hereininclude liquid, non-alkoxylated polyol polyesters (see Jandacek; U.S.Pat. No. 4,005,195; issued Jan. 25, 1977); liquid esters oftricarballylic acids (see Hamm; U.S. Pat. No. 4,508,746; issued Apr. 2,1985); liquid diesters of dicarboxylic acids such as derivatives ofmalonic and succinic acid (see Fulcher, U.S. Pat. No. 4,582,927; issuedApr. 15, 1986); liquid triglycerides of alpha-branched chain carboxylicacids (see Whyte; U.S. Pat. No. 3,579,548; issued May 18, 1971); liquidethers and ether esters containing the neopentyl moiety (see Minich;U.S. Pat. No. 2,962,419; issued Nov. 9, 1960); liquid fatty polyethersof polyglycerol (See Hunter et al; U.S. Pat. No. 3,932,532; issued Jan.13, 1976); liquid alkyl glycoside fatty acid polyesters (see Meyer etal; U.S. Pat. No. 4,840,815; issued Jun. 20, 1989); liquid polyesters oftwo ether linked hydroxypolycarboxylic acids (e.g., citric or isocitricacid) (see Huhn et al; U.S. Pat. No. 4,888,195; issued Dec. 19, 1988);as well as liquid polydimethyl siloxanes (e.g., Fluid Siliconesavailable from Dow Corning). All of the foregoing patents relating tothe liquid nondigestible oil component are incorporated herein byreference.

[0102] Preferred liquid nondigestible oils are the liquid polyolpolyesters that comprise liquid sugar polyesters, liquid sugar alcoholpolyesters, and mixtures thereof. The preferred sugars and sugaralcohols for preparing these liquid polyol polyesters includeerythritol, xylitol, sorbitol, and glucose, with sucrose beingespecially preferred. The sugar or sugar alcohol starting materials forthese liquid polyol polyesters are preferably esterified with fattyacids containing from 8 to 22 carbon atoms, and most preferably from 8to 18 carbon atoms. Suitable naturally occurring sources of such fattyacids include corn oil fatty acids, cottonseed oil fatty acids, peanutoil fatty acids, soybean oil fatty acids, canola oil fatty acids (i.e.fatty acids derived from low erucic acid rapeseed oil), sunflower seedoil fatty acids, sesame seed oil fatty acids, safflower oil fatty acids,fractionated palm oil fatty acids, palm kernel oil fatty acids, coconutoil fatty acids, tallow fatty acids and lard fatty acids.

[0103] The nondigestible polyol polyesters that are liquid are thosewhich have minimal or no solids at body temperatures (i.e., 98.6° F.,37° C.). These liquid polyol polyesters typically contain ester groupshaving a high proportion of C₁₂ or lower fatty acid radicals or else ahigh proportion of C₁₈ or higher unsaturated fatty acid radicals. In thecase of those liquid polyol polyesters having high proportions ofunsaturated C₁₈ or higher fatty acid radicals, at least about half ofthe fatty acids incorporated into the polyester molecule are typicallyunsaturated. Preferred unsaturated fatty acids in such liquid polyolpolyesters are oleic acid, linoleic acid, and mixtures thereof.

[0104] The following are nonlimiting examples of specific liquid polyolpolyesters suitable for use in the present invention: sucrosetetraoleate, sucrose pentaoleate, sucrose hexaoleate, sucroseheptaoleate, sucrose octaoleate, sucrose hepta and octaesters ofunsaturated soybean oil fatty acids, canola oil fatty acids, cottonseedoil fatty acids, corn oil fatty acids, peanut oil fatty acids, palmkernel oil fatty acids, or coconut oil fatty acids, glucose tetraoleate,the glucose tetraesters of coconut oil or unsaturated soybean oil fattyacids, the mannose tetraesters of mixed soybean oil fatty acids, thegalactose tetraesters of oleic acid, the arabinose tetraesters oflinoleic acid, xylose tetralinoleate, galactose pentaoleate, sorbitoltetraoleate, the sorbitol hexaesters of unsaturated soybean oil fattyacids, xylitol pentaoleate, and mixtures thereof.

[0105] The liquid polyol polyesters suitable for use in the compositionsherein can be prepared by a variety of methods known to those skilled inthe art. These methods include: transesterification of the polyol (i.e.sugar or sugar alcohol) with methyl, ethyl or glycerol esters containingthe desired acid radicals using a variety of catalysts; acylation of thepolyol with an acid chloride; acylation of the polyol with an acidanhydride; and acylation of the polyol with the desired acid, per se.(See, for example, U.S. Pat. Nos. 2,831,854, 3,600,186. 3,963,699,4,517,360 and 4,518,772, all of which are incorporated by reference.These patents all disclose suitable methods for preparing polyolpolyesters.)

[0106] C. Other Shortening Ingredients

[0107] So long as they do not interfere with the formation of theflowable nondigestible oil, the flowable nondigestible oil compositionsmay also comprise other shortening ingredients. Various additives can beused herein provided they are edible and aesthetically desirable and donot have any detrimental effects on the shortenings. These additivesinclude edible, digestible oils and hardstock, fat-soluble vitamins,flavorings and seasonings, emulsifiers, anti-spattering agents,chelating agents, anti-sticking agents, anti-oxidants, anti-foamingagents (for frying applications) or the like.

[0108] D. Formation of Stiffened Nondigestible Oil

[0109] The nondigestible oil composition described herein is capable ofcrystallizing from a molten liquid form to a stiffened nonflowable oilform when the nondigestible oil composition is rapidly cooled from themolten temperature to the crystallization temperature of the solidpolyol polyester, or less (for example, to body temperature, about 37°C.) under substantially quiescent conditions. This stiffened nonflowablenondigestible oil comprises the liquid nondigestible oil portionretained substantially completely within the crystalline matrix ofcrystallized solid polyol fatty acid polyester, thereby providing thedesired passive oil loss control of the nondigestible oil. Thecomposition and method of making of the food composition should beselected to provide the sufficiently rapid cooling of the nondigestibleoil from a molten temperature to a lower temperature substantially inthe absence of shearing of the food composition, such that the solidpolyol fatty acid polyester has crystallized into the desiredcrystalline form which provides the desired passive oil loss control.Generally, this cooling rate from the onset crystallization temperatureof the highest melting solid polyol fatty acid polyester to thecrystallization temperature (of the lowest melting solid polyol fattyacid polyester component) is greater than about 0.5° C./min, morepreferably greater than about 2.5° C./min, and most preferably greaterthan 25° C./min. In the case of a polyol polyester polymer, which canform the desired crystal structure for passive oil loss control at muchslower cooling rates, a cooling rate of greater than about 0.03° C./min.under the quiescent conditions is generally sufficient to form thedesired crystal structure.

[0110] When a nondigestible oil composition comprising a solid polyolfatty acid polyester containing any one or a combination of a solidsaturated polyol polyester, a solid diversely esterified polyolpolyester, and a polyol polyester polymer, begin to crystallize (orco-crystallize) in the liquid polyol polyester, the crystals (orco-crystals) initially appear as discrete, unaggregated entities,suspended in the liquid polyol fatty acid polyester. Under quiescentcooling conditions, such as when the molten nondigestible oil has beenprocessed into food products via baking or frying, these discreteunaggregated entities can grow as crystallization continues, and beginto cluster together to form small aggregates of at least 3 microns,dispersed in the liquid nondigestible oil. These small aggregateclusters of particles can develop in a variety of forms and shapes,including spherical, platelet-like, filament-like or rod-like, orcombinations of these various shapes, but are typically spherical orplatelet-like. Thinner aggregate particles, referred to as platelets,are preferred from the standpoint of providing more efficient passiveoil loss control of the liquid polyol polyester component of thenondigestible oil compositions herein. These platelet particlespreferably have a thickness of about 0.1 micron or less, more preferablyabout 0.05 micron or less. As the crystallization continues, theplatelets continue to grow and to cluster together to form a largeraggregate particle that is porous in character and thus capable ofentrapping significant amounts of the liquid polyol polyester. It isbelieved that this porous structure and its concomitant ability toentrap large amounts of liquid polyol polyester is why these largeraggregated, platelet-like particles can provide very effective andefficient passive oil loss control, and results in a stiffened,nonflowable nondigestible oil.

[0111] II. Process for Making a Flowable Nondigestible Oil Composition:

[0112] The present invention also provides a process for making aflowable nondigestible oil composition comprising a liquid componenthaving a complete melt point less than 37° C., and a solid componenthaving a complete melt point of at least about 37° C. The processcomprises the steps of:

[0113] a) providing a mixture comprising the liquid component and thesolid component, wherein at least one of the liquid component and thesolid comprises a material selected from esterified linked alkoxylatedpolyols, such as esterified linked alkoxylated glycerines; esterifiedepoxide-extended polyols; and mixtures thereof;

[0114] b) melting the mixture of the liquid component and the solidcomponent;

[0115] c) crystallizing at least a substantial portion of the solidcomponent; and

[0116] d) shearing the mixture of the liquid component and the solidcomponent during the step of crystallizing, thereby forming at least asubstantial portion of the solid component into crystallized particles.

[0117] According to one embodiment, the process comprises the steps ofmelting completely the mixture containing the solid component, rapidlycooling the melted mixture to a crystallization temperature, therebyrapidly crystallizing at least a substantial portion of the solidcomponent, and shearing the mixture during the step of crystallizing toform the flowable nondigestible oil composition. Optionally, followingthe crystallizing and shearing steps, the process can include one orboth of the following steps: 1) the step of tempering the crystallizednondigestible oil composition for a time sufficient to substantiallycompletely crystallize all of the solid component, and/or 2) the step ofadding a stabilizing amount of a diluent liquid, typically a liquidpolyol fatty acid polyester, to the crystallized nondigestible oilcomposition, or both steps.

[0118] The process of the present invention for making a flowablenondigestible oil typically requires at least about 5 minutes andgenerally no more than about 3 hours, preferably at least about 5minutes and generally no more than about 2 hours, more preferably atleast about 10 minutes and no more than about 1 hour, and mostpreferably at least about 15 minutes and no more than about 30 minutes.

[0119] Without the invention being bound by any theory ofcrystallization described herein, it is understood that crystallizationof the solid component occurs kinetically. As with any kinetic reaction,a dynamic equilibrium can be achieved wherein the reaction may appear tohave halted. Then, by changing the conditions, the reaction can be madeto proceed forward, or even to reverse. In the same way, the solidcomponent can crystallize under a condition until a dynamic equilibriumis achieved. The dynamic equilibrium can exist wherein a portion of asolid component is still dissolved in the liquid component while thepreponderance has been crystallized. The rate at which a solid componentwill crystallize depends upon several factors, such as, the molecularcomposition of the solid component, the concentration of the solidcomponent, the proportion of solid component already crystallized tothat remaining dissolved in the liquid component, and the temperaturedifferential between the onset crystallization temperature of the solidcomponent and the temperature of crystallization.

[0120] At the onset of crystallization, the solid component willinitially crystallize at a high crystallization rate. Thiscrystallization rate slows with time, eventually (ideally) to a rate ofzero. Then, when the mixture of the solid and liquid components isfurther cooled to a lower temperature the equilibrium is shifted suchthat, for instance, it is possible that additional solid polyol fattyacid polyester can crystallize from the liquid polyol polyester. Whilethe proportion of solid polyol fatty acid polyester which willcrystallize with an incremental reduction in temperature is generallylow, it is believed that additional crystallizing solid polyol fattyacid polyester will, in the absence of shearing, tend to crystallize asdiscrete, unaggregated entities suspended in the liquid polyol fattyacid polyester or onto other aggregate particles. The discreteunaggregated entities may begin to cluster together to form smallaggregates, typically up to several microns in size. However, in thepresence of applied shear, these unaggregated entities generally do notform into aggregate particles, and any aggregate particles that mightform do not generally continue to cluster into a large matrix of crystalaggregate, thereby promoting the flowability of the nondigestible oil.

[0121] The flowable nondigestible oil composition of the presentinvention can be processed using crystallization and mixing equipmentthat is commonly employed to crystallize fats. Both batch and continuousprocessing systems and equipment can be used, though a continuous systemis generally preferred. The general requirement of the system is to becapable of rapidly cooling the molten polyol polyester component to thecrystallization temperature range, and crystallizing at least asubstantial portion of the solid polyol fatty acid polyester, mostpreferably while simultaneously shearing the composition sufficiently toform the flowable nondigestible oil composition.

[0122] A. Melting of the Nondigestible Oil Composition

[0123] The first step of the process of the present invention comprisesmelting the solid component in the liquid component at a temperatureabove the temperature where the last amount of the solid component ismelted into the liquid. Preferably, the composition is raised to atemperature at least 10° C. above the complete melt temperature of thesolid component.

[0124] In the molten state, the nondigestible oil compositions aregenerally transparent and clear. It will be observed that as the solidcomponent begins to crystallize (at and below the onset crystallizationtemperature), the liquid component begins to become turbid and clouded.The “onset crystallization temperature” for the solid componentsdescribed herein can be determined by the method described below in theAnalytical section.

[0125] B. Crystallization of the Solid Component

[0126] The next step of the process comprises rapidly crystallizing atleast a substantial portion of the solid component, defined as at leastmore than 50% by weight, and preferably more than 80%, more preferablymore than 95%, and most preferably more than 99%. This step can comprisethe steps of reducing the temperature of the molten mixture of themelted solid component and the liquid component to a crystallizationtemperature of the solid component, and holding the mixture at thecrystallization temperature for a time sufficient to crystallize thesubstantial portion of the solid component.

[0127] The crystallization temperature is preferably within acrystallization temperature range of from about the onsetcrystallization temperature of the solid component, down to about 25°C., preferably down to about 10° C. Where the solid component containstwo or more distinct materials, such as two distinct solid polyol fattyacid polyester materials having different onset melting temperatures,preferably the crystallization temperature is below the lowest onsettemperature thereof, and preferably at least about 5° C., morepreferably at least about 10° C., below the lowest onset crystallizationtemperature. Most preferably, the crystallization temperature (or lowestcrystallization temperature if there are multiple solid materials) iswithin the temperature range of the storage conditions for the flowablenondigestible oil, such storage temperature range typically being about15° C. to about 40° C., and more particularly about 25° C. to about 30°C. It should be understood that the rate of crystallization of the solidcomponent will be higher as the crystallization temperature is reducedlower below the onset crystallization temperature of the solidcomponent.

[0128] The step of rapidly crystallizing the substantial portion of thesolid component can be completed in less than about 30 minutes,preferably in less than about 5 minutes, and more preferably in lessthan about 30 seconds, and most preferably in less than about 15seconds. Generally about 5 seconds to about 30 seconds are neededdepending upon the type of equipment used. While the step can becompleted within a period of time of more than 30 minutes, suchadditional time is understood to provide no particular additionalbenefits.

[0129] The process also comprises the step of shearing during the stepof crystallizing the solid component at the crystallization temperature.By applying shear to the composition during the crystallization, thesolid component is encouraged to crystallize into discrete crystals andunaggregated crystal platelets. By shearing while the crystallization isoccurring, the resulting discrete and unaggregated crystals can beinhibited from growing to a size that might be large enough to separatefrom the liquid phase. It is also believed that the small crystalplatelets may aggregate into small aggregate particles, but that theshearing inhibits the small aggregate particles from further clusteringinto larger aggregate particles which can begin to stiffen thecomposition. During the crystallizing step, shear is imparted to themixture at from about 400 sec⁻¹ to about 8000 sec⁻¹, more preferably atfrom about 500 sec⁻¹ to about 6000 sec⁻¹.

[0130] The crystallizing step can be conducted in such equipment as aswept-wall, scraped-wall, or screw-type heat exchanger or equivalent,scraped wall agitated reactors, plate and frame heat exchangers, andtube and shell heat exchangers. Such equipment in general cools thecomposition at a rate of from about 0.4° C./min. to 300° C./min., morepreferably from about 0.8° C./min. to about 150° C./min. Examples ofsuch heat exchangers include Cherry Burrell Votator, Girdler “A” units,a Sollich Turbo Temperer, and a Groen Model #DR(C) used for margarineand shortening manufacture, and Aasted chocolate tempering units. Apreferred unit is the Votator unit which consists of a steel shaftrotating in a tube which is cooled externally by a coolant. The rotatingshaft is fitted with scraper blades which press against the cool innersurface at high rotation speeds, continuously scraping the crystallizingcomposition from the inner surface of the tube. References to theseconventional units include: Greenwell, B. A., J. Amer. Oil Chem. Soc.,March 1981, pp. 206-7; Haighton, A. J., J. Amer. Oil Chem. Soc., 1976,Vol. 53, pp. 397-9; Wiedermann, L. H. J. Amer. Oil Chem. Soc., Vol. 55,pp. 826-7; Beckett, S. T., editor, Industrial Chocolate Manufacture andUse, Van Nostrand Reinhold, New York, 1988, pp. 185-9. All of thesepublications are incorporated herein by reference.

[0131] A scraped wall heat exchanger is a preferred apparatus forrapidly reducing the temperature and providing crystallization underhigh shear, typically at temperature reduction rates of about 8-300°C./min., and preferably about 100-300° C./min. The temperature of thecoolant used for this crystallizing step in this equipment issufficiently low to quickly cool the mixture, but not so low so as tocause a significant amount of plating out of the solid component ontothe chilled surfaces of the apparatus. Typically the coolant temperatureis in the range of from about −23° C. to about 20° C., more preferablyin the range of from about −6.7° C. to about 7° C. Typical coolantsinclude liquid ammonia, brine, and other refrigerants.

[0132] The melted mixture can also be precooled before entering thescraped wall heat exchanger, to a temperature not far above the onsetcrystallization temperature of the solid component, using a separateheat exchanger.

[0133] In general, the rate of shearing to be applied to the compositionduring the crystallization step should be commensurate with the rate ofcrystallization of the solid component. That is, for example, when thecrystallization temperature is set well below the onset crystallizationtemperature such that the rate of crystallization is very high; thenhigher rates of shearing are needed to form the desired crystal plateletparticles. Of course, if the crystallization rate greatly exceeds theshearing rate, such that large aggregate particles are formed in thecomposition, the shearing can be continued after crystallization hasslowed or stopped to effect a reduction in the large aggregate particlesand a resulting more flowable composition, by the breaking and tearingof the large aggregate particles by the force of shear.

[0134] Following the step of rapidly crystallizing and shearing themixture to form the discrete and unaggregated crystal particles, it ispreferred to continue shearing the crystallized composition at thecrystallization temperature for a time sufficient for crystallization ofthe solid component to come substantially to completion, and to allowthe solid component to complete crystallization to the discrete andunaggregated crystal particles. The continued shearing step serves todisrupt the formation of larger aggregate particles and anythree-dimensional crystalline matrix that otherwise can form from thelarger aggregate particles in the absence of the shearing. Suchcontinued shearing preferably avoids creating any dead zones in themixing vessel which might resulting in a localized stiffenedcomposition. Typically the continued shearing is done for at least about2 seconds, preferably for about 5 minutes, and more preferably for atleast about 10 minutes. Generally no more than about 2 hours, preferablyabout no more than 1 hour, more preferably no more than about 30minutes, is required for the continued shearing step.

[0135] In the continued shearing step, generally less shear is needed incomparison with that used during the crystallization step. Generallyduring the continued shearing step, shear rates range from about 10sec⁻¹ to about 8000 sec⁻¹. Preferred types of apparatus for carrying outthe continued shearing step include any agitated, jacketed vesselcapable of being operated such that preferably air can be excluded fromincorporation into the polyol polyester composition, and the temperatureof the composition can be suitably controlled. An example of a suitablescraped-wall, jacketed, open tank mixer is a Krueter temper kettle(Beckett, pp. 183-4). In addition, it is possible to carry out theconditioning step in two or more separate pieces of agitated, heatexchanger equipment. Another mechanical devices that can be used for thecontinued shearing of the crystallized polyol polyester is a Ross 410 X3or a Readco twin screw mixer.

[0136] The continued shearing step can also be accomplished usingnon-mechanical mixing devices such as static mixers, consisting of apipe section having a plurality of mixing elements contained in a seriestherein. Turbulence and shear are imparted to the product as it passesthrough stationary mixing blades within the pipe. Manufacturers ofin-line static mixer include Komax and Lightnin.

[0137] It is also possible to carry out both the crystallizing step andany continued shearing step in a single piece of equipment, such as, forexample, in a turbo temperer such as a Sollich Turbo Tempering column.

[0138] C. Tempering

[0139] The process of the present invention can optionally include atempering step. The tempering step comprises reducing the temperature ofthe crystallized mixture to a tempering temperature that is less thanthe intended minimum handling and storage temperature of the flowablenondigestible composition, and holding the composition at the temperingtemperature for a time sufficient to substantially completecrystallizatioin. A tempering step can advantageously be employed whenthe crystallization temperature of the crystallizing step is above theintended storage temperature of the flowable nondigestible composition.The tempering step is usually not required when the crystallizationtemperature is itself below the intended storage temperature. Thetempering temperature is preferably at least 5° C., more preferably atleast 10° C., below the intended ambient handling/storage temperature ofthe flowable nondigestible composition. Typically, the temperingtemperature is from about 5° C. to about 25° C., preferably about 5° C.to about 15° C.

[0140] In order to prevent the aggregation of crystallized particlesduring the tempering step, shear mixing should be applied to themixture. In general the tempering step will take from about 2 minutes toabout 2 hours, preferably from about 2 minutes to about 1 hour, morepreferably about 5 minutes to about 20 minutes. The amount of shearingthat is typically provided in the tempering step will be substantial thesame as that provided during the crystallization step, though preferablyit is at least about 1 sec⁻¹, and preferably about 25 sec⁻¹ to about 50sec⁻¹. As with the continued shearing, the tempering step should avoidcreating any dead zones in the mixing vessel which might result in alocalized stiffened composition.

[0141] Following the tempering step, the flowable nondigestibiecomposition is preferably raised in temperature to the ambienthandling/storage temperature.

[0142] D. Diluent Addition

[0143] The process of the present invention can also optionally includea step of adding an amount of, and preferably a stabilizing amount of, adiluent liquid to the crystallized mixture in order to form, andpreferably to ensure the stability of, the resulting flowablenondigestible composition. The principle of adding a diluent liquid isto increase incrementally the solubility of the solid component into theliquid component, thereby promoting a more flowable composition.Preferably the diluent liquid is added after the crystallizationtemperature has been reduced to the ambient storage temperature, evenmore preferably after any tempering step. The addition of the diluentcan reduce, and preferably stop, the driving force which promotescrystillization of the solid out of solution, and can even result insome amount of re-solubilizing of crystallized solid polyol polyesterback into the liquid phase. The diluent is added in an amount, relativeto the amount of the processed nondigestible oil after tempering,generally at about 10:1 to about 0.01:1, preferably about 2:1 to about0.01:1, more preferably about 1:1 to about 0.05:1, and most preferablyabout 0.5:1 to about 0.1:1. The temperature of the diluent liquid isfrom about 5° C. to about 50° C., more preferably about 10° C. to about25° C., when it is added to the crystillized mixture. The temperature ofthe diluent liquid will depend upon the amount of diluent liquid used,the preferred storage temperature of the flowable nondigestible oil, andother factors that will be understood by one skilled in the art.

[0144] The liquid diluent can comprise liquid polyol polyesters,including alkoxylated and non-alkoxylated polyol polyesters. A preferreddiluent is a liquid having the same composition as the liquid componentused to form the flowable nondigestible composition, however, anysuitable combination of solid component, liquid component, and liquiddiluent can be used. For instance, if the liquid component comprises aliquid esterified linked alkoxylated polyol, the liquid diluent cancomprise the same liquid esterified linked alkoxylated polyol, adifferent esterified linked alkoxylated polyol, or a non-alkoxylatedliquid polyol, such as sucrose polyester. Other diluents can be otheredible oils, preferably nondigestible oils, which are miscible with theliquid component of the flowable nondigestible composition, and aregenerally lipophilic.

[0145] If the flowable nondigestible oil composition is permitted to setwithout any circulation or stirring for an extended period of time, itis possible that minor temperature fluctuations could result in anincremental crystallization of remaining solid component in the liquidcomponent, which could result in a thickening and stiffening of thecomposition. Application of additional shear, therefore, would serve tobreak up any larger aggregate particles that may have formed from theclustering of small aggregate particles, thereby reducing theConsistency of the composition.

[0146] The step of adding the diluent liquid to the crystallized mixturecan be before any continued shearing of the crystallized mixture orafter any continued shearing step. The adding of the diluent liquidbefore the continued shearing step reduces the time needed for thecontinued shearing.

[0147] III. Temperature Sensitive Food Additives

[0148] The flowable nondigestible oil composition can further comprisetemperature sensitive food additives, including fat-soluble and othervitamins, flavorings, and seasonings. The food additives can be addedeither as a particulate or as a liquid. When adding as a particulate,the particulate food additive can be added to the final flowablenondigestible oil, or added during the crystallization of thecompositions at a step where the temperature does not adversely effectthe efficacy of the additive.

[0149] The present flowable nondigestible oil compositions can also befortified with vitamins and minerals, particularly the fat-solublevitamins. The fat-soluble vitamins include vitamin A, vitamin D, vitaminK, and vitamin E. (See U.S. Pat. No. 4,034,083 (Mattson) issued Jul. 5,1977, incorporated by reference herein.)

[0150] IV. Uses of the Non-digestible Oil Compositions

[0151] The nondigestible oils, which can be processed into the flowablenondigestible oils of the present invention, can be used in flyingapplications such as the preparation of French fried potatoes, potatochips, corn chips, tortilla chips, chicken, fish, and battered and friedfoods (e.g. shrimp tempura). Preferably, the compositions can be used asshortenings, cooking oils, frying oils, salad oils, and popcorn oils.The compositions may also be used in cooking sprays, margarines andspreads. The individual composition components may be mixed beforepreparing foods or they can be added separately to the foods.

[0152] The nondigestible oils can also be used in the production ofbaked goods in any form, such as mixes, shelf-stable baked goods, andfrozen baked goods. Possible applications include, but are not limitedto, cakes, brownies, muffins, bar cookies, wafers, biscuits, pastries,pies, pie crusts, granola bars, and cookies, including sandwich cookiesand chocolate chip cookies, particularly the storage-stabledual-textured cookies described in U.S. Pat. No. 4,455,333 of Hong &Brabbs. The baked goods can contain fruit, cream, or other fillings.Other baked good uses include breads and rolls, crackers, pretzels,pancakes, waffles, ice cream cones and cups, yeast-raised baked goods,pizzas and pizza crusts, and baked farinaceous snack foods, and otherbaked salted snacks.

[0153] The herein can also be used as a component of the fat portion ofmany other foods such as ice cream, frozen desserts, cheese, meats,chocolate confections, salad dressings, mayonnaise, margarine, spreads,sour cream, yogurt, coffee creamer, extruded snacks, roasted nuts andbeverages, such as milk shakes.

[0154] The compositions of the present invention can be used tosubstitute from about 10% to 100% of the fat/oil in foods. Whensubstituting the present compositions for fat in foods which contain fatand nonfat ingredients (e.g., starches, sugar, nonfat milk solids, etc.)the solid polyol polyesters are included to control passive oil loss ofthe nondigestible oil when said foods are ingested.

[0155] The compositions herein can be used in combination with othernondigestible fats, such as branched chain fatty acid triglycerides,triglycerol ethers, polycarboxylic acid esters, sucrose polyethers,neopentyl alcohol esters, silicone oils/siloxanes, and dicarboxylic acidesters. Other partial fat replacements useful in combination with thematerials herein are medium chain triglycerides, triglycerides made withcombinations of medium and long chain fatty acids (like the onesdescribed in European Application 0322027 (Seiden), published Jun. 28,1989, incorporated herein by reference), highly esterified polyglycerolesters, acetin fats, plant sterol esters, polyoxyethylene esters, jojobaesters, mono/diglycerides of fatty acids, and mono/diglycerides ofshort-chain dibasic acids.

[0156] The compositions are particularly useful in combination withparticular classes of food and beverage ingredients. For example, anextra calorie reduction benefit is achieved when the present flowableshortenings are used with noncaloric or reduced calorie sweeteners aloneor in combination with bulking agents. Noncaloric or reduced caloriesweeteners include, but are not limited to, aspartame, saccharin,alitame, thaumatin, dihydrochalcones, acesulfame and cyclamates.

[0157] Bulking or bodying agents are useful in combination with thenondigestible oil compositions herein in many food compositions. Thebulking agents can be nondigestible carbohydrates, for example,polydextrose and cellulose or cellulose derivatives, such ascarboxymethylcellulose, carboxyethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, methyl cellulose andmicrocrystalline cellulose. Other suitable bulking agents include gums(hydrocolloids), starches, dextrins, fermented whey, tofu,maltodextrins, polyols, including sugar alcohols, e.g., sorbitol andmannitol, and carbohydrates, e.g., lactose.

[0158] Similarly, food and beverage compositions can be made thatcombine the present nondigestible oil compositions with dietary fibersto achieve the combined benefits of each. By “dietary fiber” is meantcomplex carbohydrates resistant to digestion by mammalian enzymes, suchas the carbohydrates found in plant cell walls and seaweed, and thoseproduced by microbial fermentation. Examples of these complexcarbohydrates are brans, celluloses, hemicelluloses, pectins, gums andmucilages, seaweed extract, and biosynthetic gums. Sources of thecellulosic fiber include vegetables, fruits, seeds, cereals, and manmadefibers (for example, by bacterial synthesis). Commercial fibers such aspurified plant cellulose, or cellulose flour, can also be used.Naturally occurring fibers, such as psyllium, and fibers from wholecitrus peel, citrus albedo, sugar beets, citrus pulp and vesicle solids,apples, apricots, and watermelon rinds.

[0159] These dietary fibers may be in a crude or purified form. Thedietary fiber used may be of a single type (e.g., cellulose), acomposite dietary fiber (e.g., citrus albedo fiber containing celluloseand pectin), or some combination of fibers (e.g., cellulose and a gum).The fibers can be processed by methods known to the art.

[0160] Of course, judgment must be exercised to make use of the presentcompositions and combinations thereof with other food ingredients. Forexample, a combination of sweetener and present flowable compositionswould not be used where the specific benefits of the two are notdesired. The composition and flowable composition/ingredientcombinations are used where appropriate, and in appropriate amounts.

[0161] Many benefits are obtained from the use of the thesenondigestible oil composition in food and beverage compositions, eitherwhen used alone or in combination with edible oils and/or otheringredients discussed above. A primary benefit is the calorie reductionachieved when nondigestible oil compositions are used as a total orpartial fat replacement. This calorie reduction can be increased byusing combinations of the present nondigestible oil compositions withreduced calorie sweeteners, bulking agents, or other nondigestible fatsand oils. Another benefit which follows from this use is a decrease inthe total amount of digestible fats in the diet. Furthermore, asignificant reduction in saturated fat consumption can be achieved bysubstituting the present nondigestible oil compositions for saturatedfats in the diet. Foods or beverages made with the nondigestible solidfat materials instead of animal-derived triglyceride fats will alsocontain less cholesterol, and the ingestion of these foods can lead toreduced serum cholesterol and thus reduced risk of heart disease. Also,compositions made with these fat materials have acceptable organolepticproperties, particularly lack of waxiness.

[0162] Dietary foods can be made with the nondigestible oilcompositions, to meet special dietary needs, for example, of persons whoare obese, diabetic, or hypercholesterolemic. The present compositionscan be a major part of a low-fat, low-calorie, low-cholesterol diet, andthey can be used alone or in combination with drug therapy or othertherapy. Combinations of food or beverage products made with the presentnondigestible oil compositions can be used as part of a total dietarymanagement regimen, based on one or more of these products, containingthe fat materials alone or in combination with one or more of theabove-mentioned ingredients, to provide one or more of theabove-mentioned benefits.

[0163] This discussion of the present nondigestible oil compositionuses, combinations, and benefits is not intended to be limiting orall-inclusive. It is contemplated that other similar uses and benefitscan be found that will fall within the spirit and scope of thisinvention.

[0164] In addition to food compositions, the flowable or nonflowablenondigestible oil compositions of the present invention can be used informulating lubricants, skin creams, pharmaceuticals, cosmetics, and thelike.

[0165] The invention will be illustrated by the examples which followthe analytical methods.

[0166] V. Processing of Flowable Nondizestible Oil into Food andBeverage Products

[0167] The present flowable compositions are useful in the preparationof a wide variety of food and beverage products. Because of theprocessing steps in the present invention, the resulting flowablenondigestible oil composition, if consumed in its form directly or infoods containing the flowable nondigestible oil, may have relativelypoor passive oil loss control. Consequently, it is important first tocompletely melt the flowable nondigestible oil to a completely moltennondigestible oil, such that the crystallized solid component, such asthe solid polyol fatty acid polyester, is substantially completelymelted. Preferably, the flowable nondigestible oil is melted up to atemperature of about 10° C. or more above the complete melt point of thesolid component. The molten nondigestible oil can then be processed intofood and beverage compositions in a manner that provides sufficientlyrapid cooling of the nondigestible oil in a substantially quiescentstate (that is, without applying shear during the crystallization) toyield a solid polyol polyester crystalline structure that provides goodpassive oil loss control.

[0168] Alternatively, the flowable nondigestible oil can be applied intothe food-making process directly, so long as the processing results in asubstantially complete melting of the solid polyol fatty acid polyester,and subsequent rapid cooling of the molten nondigestible oil to providethe good passive oil loss control. An example of such a process isspraying of the flowable nondigestible oil onto the surface of a snackfood just after frying or baking. Because the snack food is still hot,the flowable nondigestible oil will be substantially completely melted,including the solid polyol fatty acid polyester thereof, and willsubsequently crystallize into a form displaying passive oil loss controlas the snack food cools rapidly.

[0169] When the flowable nondigestible oil composition comprises atemperature sensitive food additive, such as a vitamin, then it isimportant that the time during which the nondigestible oil compositionis in its remelted state should be kept to a minimum to avoid loss ofefficacy of the vitamin.

[0170] VI. Analytical Methods

[0171] (a). Solid Fat Content

[0172] Before determining Solid Fat Content (SFC) values, a sample ofthe flowable composition or mixture of nondigestible liquid/solid isheated to a temperature of 140° F. (60° C.) or higher for at least 30minutes or until the sample is completely melted. The melted sample isthen tempered as follows: at 80° F. (26.7° C.) for 15 minutes; at 32° F.(0° C.) for 15 minutes; at 80° F. (26.7° C.) for 30 minutes; and at 32°F. (0° C.) for 15 minutes. After tempering, the SFC values of the sampleat temperatures of 50° F. (10° C.), 70° F. (21.1° C.), 80° F. (26.7°C.), 92° F. (33.3° C.) and 98.6° F. (37° C.), can be determined bypulsed nuclear magnetic resonance (PNMR) after equilibration for 30minutes at each temperature. The method for determining SFC values byPNMR is described in Madison and Hill, J. Amer. Oil Chem. Soc., Vol. 55(1978), pp. 328-31 (herein incorporated by reference). Measurement ofSFC by PNMR is also described in A.O.C.S. Official Method Cd. 16-81,Official Methods and Recommended Practices of The American Oil ChemistsSociety, 3rd. Ed.. 1987 (herein incorporated by reference).

[0173] The slope of the SFC profile is calculated by subtracting thepercent solids at 70° F. from the percent solids at 98.6° F. anddividing that value by 28.6.

[0174] (b). Consistency

[0175] The Consistency (K) of the nondigestible oil is measured at atemperature between 20 and 40° C. using a Rheometrics controlled stressrheometer equipped with a cone and plate measuring system. The conediameter is 4 cm and the cone angle is 2 degrees. A sample of thenondigestible oil is carefully applied to the plate and the cone is thenslowly lowered onto the sample (gap=0.048 mm). A flow measurement isperformed via the programmed application of a shear stress over time.The shear stress is increased from zero to 5,000 dynes/cm² over a 2minutes time span. The applied stress results in deformation of thesample (i.e., strain) and the rate of strain is reported as a shearrate. These data are used to create a flow curve of log [apparentviscosity] versus log [shear rate] for the nondigestible oil sample. Theflow curve is then modeled according to the following power law model:

Apparent Viscosity=K (Shear Rate)^(n−1)

[0176] where the apparent viscosity is expressed in units of poise (P),shear rate is in units of 1/sec, K is the Consistency in units ofP.sec^((n−1)), and n is the shear index (dimensionless). The power lawmodel is widely used to describe the flow behavior of non-newtonianmaterials. On the log-log plot of apparent viscosity versus shear rate,the power law model is a straight line with slope of (n−1). The shearindex (n) varies from 0 to 1. The closer n is to 1, the closer thematerial's flow behavior is to newtonian behavior. The Consistency (K)is numerically equal to the apparent viscosity at a shear rate of 1sec⁻¹. The values of K and n describe the flow behavior of thenondigestible oil within specific limits of shear.

[0177] (c). Crystallization Onset Temperature

[0178] The crystallization onset temperature is that temperature atwhich, under the conditions of this test, turbidity is induced in thesample within 90 minutes after reaching and maintaining thecrystallization onset temperature. Turbidity is caused by the firststage of crystallization.

[0179] Apparatus:

[0180] 1. Jacketed, agitated, cylindrical glass flask, 4 inches indiameter, at least 250 ml volume. Heating and cooling are accomplishedby circulation of a clear, uncolored fluid through the jacket.Acceptable jacket fluids are, but are not limited to, water, ethyleneglycol, or silicone fluids.

[0181] 2. Thermometer, calibrated in the range 25° C. to 100° C.

[0182] Procedure:

[0183] 1. In the flask, heat at least 250 ml of sample (but not morethan 700 ml) to 85° C. and hold until all solids have dissolved. Beforeproceeding, the solution must be clear, without any turbidity.

[0184] 2. Agitate to maintain uniform temperature throughout the flask.

[0185] 3. Cool at no more than 2.5° C. /min to a temperature in thevicinity of the crystallization onset temperature. Note: To preventcrystallization on the vessel walls during cooling, the jackettemperature should never be any colder than 5° C. below the sampletemperature.

[0186] 4. Hold at this temperature for 90 minutes or until the clearsolution shows (by viewing horizontally through the vessel wall) thefirst hint of turbidity.

[0187] 5. If the solution becomes turbid within 90 minutes, repeat byheating and re-dissolving the sample as in step 1. Repeat steps 2, 3,and 4, except cool to a temperature 2° C. above the previousmeasurement.

[0188] 6. Repeat until the solution does not become turbid within 90minutes of reaching the test temperature. The crystallization onsettemperature is the highest temperature at which the solution becomesturbid within 90 minutes.

[0189] 7. If, on the first measurement, after 90 minutes the solutionremains clear, repeat by beating and re-dissolving the sample as in step1. Repeat steps 2, 3, and 4, except cool to a temperature 2° C. belowthe previous measurement. The crystallization onset temperature is thehighest temperature at which the solution becomes turbid within 90minutes.

[0190] (d). Fatty Acid Composition of Polyol Polyesters

[0191] The fatty acid composition (FAC) of the polyol polyesters isdetermined by gas chromatography, using a Hewlett-Packard Model S712Agas chromatograph equipped with a flame ionization detector and aHewlett-Packard Model 17671A automatic sampler. The chromatographicmethod used is described in Official Methods and Recommended Practicesof the American Oil Chemists Society, 3rd Ed., 1984, Procedure 1-Ce62(incorporated herein by reference).

[0192] (e). Ester Distribution of Sucrose Polyesters

[0193] The relative distribution of the individual octa-, hepta-, hexa-and penta- esters, as well as collectively the tetra- throughmonoesters, of the sucrose polyesters can be determined usingnormal-phase high performance liquid chromatography (HPLC). A silicagel-packed column is used in this method to separate the polyestersample into the respective ester groupings noted above. Hexane andmethyl-t-butyl ether are used as the mobile phase solvents. The estergroupings are quantitated using a mass detector (i.e. an evaporativelight-scattering detector). The detector response is measured and thennormalized to 100%. The individual ester groups are expressed as arelative percentage.

[0194] (f). Complete Melt Point

[0195] Equipment:

[0196] Perkin-Elmer 7 Series Thermal Analysis System, Model DSC7,manufactured by Perkin-Elmer, Norwalk, Conn.

[0197] Procedure:

[0198] 1) Sample of polyol polyester is heated to at least 10° C. abovethe temperature at which all visible solids are melted, and mixedthoroughly.

[0199] 2) 10±2 mg. of sample is weighed into sample pan.

[0200] 3) A scan is performed from about 10° C. above the temperature atwhich all visible solids are melted, to −60° C. at 5° C. per minute.

[0201] 4) The temperature of the sample is maintained at −60° C. for 3minutes and scanned from −60° C. to the original starting temperature at5° C. per minute (i.e. about 10° C. above the temperature at which allvisible solids are melted).

[0202] 5) The complete melting point is the temperature at theintersection of the baseline (i.e., specific heat line) with the linetangent to the trailing edge of the last (highest temperature)endothermic peak.

[0203] (g). Thickness of Solid Polyol Fatty Acid Polyester Particles(Light Microscopy)

[0204] The thickness of the solid polyol polyester particles formed inthe flowable nondigestible oil compositions herein may estimated at roomtemperature with a Nikon Microphot video-enhanced light microscope(VELM) using Hoffman Modulation Contrast (HMC) optics according to thefollowing method:

[0205] 1. A small portion (i.e., 1-10 mg) of the nondigestible oilsample with the solid polyol fatty acid polyester particles dispersedtherein is placed on a microscope slide and covered. The slide is placedunder the microscope.

[0206] 2. The sample is examined using a HMC 100×oil objective as thestandard lens in conjunction with a 10× eyepiece lens.

[0207] 3. A microscope-mounted video camera and associated controllerare used for video enhancement to facilitate differentiation between thesample and the background.

[0208] 4. The thickness of the solid polyol fatty acid polyesterparticles is measured in um (microns).

[0209] This method permits differentiation of particles havingthicknesses just within the resolution of the VELM (approximately0.2-0.5 um). Particle thickness of particles having smaller dimensionscan be determined by the Freeze Fracture Method described hereinafter.

[0210] (Note: No special sample preparation is required, other thanobtaining a representative sample. The samples should be melted andcooled ambiently.) Reference: Robert Hoffinan, “The Modulation ContrastMicroscope: Principles and Performances”, Journal of Microscopy, Vol.110, Pt 3, August 1977, pp. 205-222.

[0211] (h). Thickness of Solid Polyol Fatty Acid Polyester Particles(Freeze Fracture Transmission Electron Microscopy)

[0212] The three-dimensional topography of particles of polyol fattyacid polyesters and their size can be determined by a freeze-fracturetransmission electron microscopy (ff-tem) method.

[0213] This freeze-fracture method is carried out as follows:

[0214] 1. The outside cavity of a freezing container is filled withliquid N₂ and the inner dewar of the freezing container is filled withliquid ethane (normal melting temperature of −172° C.). The ethane isallowed to freeze.

[0215] 2. A small amount (1-2 ul) of the nondigestible fat sample withthe solid polyol fatty acid polyester particles dispersed therein isplaced in the well of a gold-plated Balzers specimen holder. (Note: forvery fluid samples, 1-2 ul of sample is placed on a gold planchet(Balzers) and another planchet is placed on top of the first to form asandwich.)

[0216] 3. Most of the frozen ethane in the dewar is melted by insertinga metal heat sink into the dewar.

[0217] 4. Immediately after melting the ethane, the specimen holdercontaining the nondigestible fat sample is picked up using a pair oftweezers and rapidly plunged into the liquid ethane.

[0218] 5. After a few seconds, the specimen holder is removed from theethane, quickly touched to the tip of a camel's hair brush to removeexcess ethane, and immediately immersed in the liquid N₂ to keep thesample cold.

[0219] 6. The sample is transferred under liquid N² to a JEOL JFD-9000Csample holder and then transferred into the chamber of a JEOL JFD-9000Cfreeze-fracture unit. The temperature of the unit should be about −175°C. Vacuum should be at least 8×10⁻⁷ torr.

[0220] 7. A knife is cooled to a temperature of about −165° C.

[0221] 8. The sample is fractured in the JEOL chamber using thepre-cooled knife.

[0222] 9. Platinum-carbon is deposited onto the fractured sample at a45° angle for 4.5 seconds, followed by carbon deposition at a 90° anglefor 25 seconds to form a replica of the fractured sample. The highvoltage is 2500V and the current is 70 mA.

[0223] 10. The samples are removed from the freeze fracture unit andcleaned using 3 washes of chloroform.

[0224] 11. The replica is picked up on a 300 mesh copper EM grid andexamined in a transmission electron microscope.

[0225] 12. Images are recorded on negative film and positive prints aremade from the negatives.

[0226] 13. The thickness of the polyol fatty acid polyester particles ismeasured in nm.

[0227] References:

[0228] Rash, J. E. and Hudson, C. S., Freeze Fracture: Methods,Artifacts, and Interpretations, New Haven Press, New York, 1979.

[0229] Stolinski and Breathnach, Freeze Fracture Replication ofBiological Tissues, Academic Press, London, 1975.

[0230] Steinbrecht and Zierold, Cryotechniques in Biological ElectronMicroscopy, Springer-Verlag, Berlin, 1987.

[0231] (i) Ester Distribution of Alkoxylated Polyols usingSuper-critical Fluid Chromatography

[0232] The composition of the polyol ester of esterified linkedalkoxylated polyols, such as esterified linked alkoxylated glycerines;and esterified epoxide-extended polyols_ can be determined bysupercritical fluid chromatography. A sample of polyglycerol ester isfirst silylated to derivatize any unreacted hydroxyl groups. Thesilylated sample is then injected into the supercritical fluidchromatograph (SFC). The esters are separated by degree ofesterification on a DB1 capillary column and detected by a flameionization detector. The distribution of esters is calculated by peakarea from the chromatogram.

[0233] Equipment and Conditions SFC: Lee scientific series 6000supercritical fluid chromatograph or equivalent;

[0234] SFC Conditions:

[0235] A) Capillary Column

[0236] DB1, 0.2 u film, 50 u ID, 10 m. J&W Scientific

[0237] B) Temperatures

[0238] Oven—90 C.

[0239] Detector—400 C.

[0240] C) Pressure Program

[0241] 125-375 atmospheres at 10 atmospheres per minute with a finalhold time of 10 minutes.

[0242] D) CO₂

[0243] SFC grade, Scott Specialty Gases

[0244] E) Hydrogen

[0245] Approximately 30 mL/minute

[0246] F) Air

[0247] Approximately 300-350 mL/minute

[0248] G) Auxiliary Gas (Nitrogen)

[0249] Approximately 25 mL/minute

[0250] H) Syringe for SFC injection

[0251] 50 ul Hamilton

[0252] I) Vials

[0253] 2 or 4 dram Kimble Glass Fischer Scientific #03-340-1 C.

[0254] J) Hot Plate

[0255] 90 C.

[0256] K) Filter

[0257] 0.45 u Alltech Associates #2092

[0258] L) Disposable Syringe

[0259] 3.0 mL Fisher Scientific #14-823-39

[0260] Reagents BSTFA (bis(Trimethylsilyl)trifluoroacetamide) Supelco,Inc. #3-3027; TMSI (Trimethylsilylimidazole) Supelco, Inc. #3-3068;Pyridine ACS Grade MCB #PX2020-01

[0261] Analyzing the Sample

[0262] The sample is melted completely and mixed well. A disposablepipet is used to weigh 80-100 mg of sample into a four dram vial. Thesample weight is recorded. 1 mL of Pyridine and 1 mL of TMSI/BSTFAsolution (mixed 5:1) is added to the vial. The vial is capped and heatedon the hot plate at 90 C. for 15 minutes. The sample is allowed to cool.A 0.45-micron filter is placed on the end of a 3-cc disposable syringe.The derivatized standard is poured into the disposable syringe andfiltered into a GC vial. The sample is injected into the SupercriticalFluid Chromatograph.

EXAMPLES

[0263] Preparation of flowable Nnndigestible fat compositions of thepresent invention is illustrated by the following prophetic examples.

Example 1 Synthesis of a Liquid Esterified Propoxylated Glycerin

[0264] Glycerin, 992 parts, is heated with 80 parts of 85% potassiumhydroxide solution at 110°°C. and 10 mm in a reactor with a dry ice trapfor water removal until no further water is evolved. The reactor ispressurized with nitrogen and cooled to 92° C., and 3126 parts ofpropylene oxide is added on a pressure demand basis maintaining areactor pressure of 55 psi. After the propylene oxide has been added thereaction is continued for an additional 5 hours. The reactor is thencooled and purged with nitrogen. A propoxylated glycerin with a molarratio of propylene oxide to glycerin of 5:1 is obtained.

[0265] The propoxylated glycerin and soybean methyl esters are mixed ina molar ratio of methyl esters to propoxylated glycerin of 5:1. Sodiummethylate, 0.13 mole sodium methylate/mole propoxylated glycerin, isadded as additional basic catalyst. The propoxylated glycerin, soybeanmethyl esters and catalyst are heated at 150° C. for 3 hours at apressure of 10 mm Hg in a reaction flask equipped with a distilling headfor methanol. At this time the reaction mix is recatalyzed with another0.13 mole sodium methylate/mole propoxylated glycerin and heated at 150°C. for an additional 3 hours at a pressure of 10 mm Hg.

[0266] All through the purification steps, the crude reaction mix ismaintained at a temperature of 80-100 C. unless otherwise noted. Thecrude reaction mix is hydrated with 0.3% by weight water and the soap isremoved by filtration. After removing the soap, the reaction mixture iswashed with an 18% by weight water solution, the water solutioncontaining 2.8% tripotassium citrate. The water phase is separated bycentrifugation. The reaction mix is then washed a second time with 340%by weight water and the water phase is separated by centrifugation.

[0267] The mixture is then dried under vacuum, bleached with 1% silicagel and filtered. The excess methyl esters are removed on a Pope wipedfilm evaporator operating at 230 C. yielding an esterified propoxylatedglycerin containing both digestible and non-digestible components. Thefatty acid composition and ester distribution is shown in Table A.

Example 2 Synthesis pf an Esterified, Linked Alkoxylated Polyol

[0268] A propoxylated glycerin with a molar ratio of propylene oxide toglycerin of 4:1 is prepared by the method of Example 1. The residualcatalyst is not removed. Three hundred and twenty-four parts (324) ofthe combined propoxylated glycerin and catalyst is mixed with of methylbehenate (708 parts giving a 2/1 mole ratio methyl behenate topropoxylated glycerin). Sodium methylate, 0.13 mole sodiummethylate/mole propoxylated glycerin, is added as additional basiccatalyst. The propoxylated glycerin, methyl behenate and catalyst areheated at 150° C. at a pressure of 10 mm Hg in a reaction flask equippedwith a distilling head for methanol until at least 95% conversion of themethyl behenate has occurred. Dimethyl adipate (87 grams) is added andheating continued at a pressure of 100 mm HG until at least 95%conversion of the original hydroxyl groups of initial propoxylatedglycerin has occurred. The distillate comprising methanol and unreacteddimethyl adipate is periodically collected and the methanol removed on arotovap. The unreacted dimethyl adipate is recycled to the reaction.

[0269] All through the purification steps, the crude reaction mix ismaintained at a temperature of 80-100 C. unless otherwise noted. Thecrude reaction mix is hydrated with 0.3% by weight water and the soap isremoved by filtration. After removing the soap, the reaction mixture iswashed with an 18% by weight water solution, the water solutioncontaining 2.8% tripotassium citrate. The water phase is separated bycentrifugation. The reaction mix is then washed a second time with 340%by weight water and the water phase is separated by centrifugation.

[0270] The mixture is then dried under vacuum, bleached with 1% silicagel and filtered. The excess methyl esters are removed on a Pope wipedfilm evaporator operating at 240 C. The fatty acid composition is shownin Table A.

Example 3 Flowable Liquid Polyol Polyester and Solid Polyol PolyesterMixture

[0271] Three mixtures are made. Mixture A contains a solid sucrosepolyester having fatty acid composition and ester distribution typicalof those shown in Table A for the product Olean® manufactured by TheProcter & Gamble Company, Cincinnati, Ohio, and a liquid esterifiedpropoxylated glycerin from Example 1. Mixture B consists of a solidesterified linked propoxylated glycerin from Example 2 and a liquidsucrose polyester having fatty acid composition and ester distributiontypical of those shown in Table A for the product Olean® manufactured byThe Procter & Gamble Company, Cincinnati, Ohio. Mixture C consists of asolid esterified linked propoxylated glycerin from Example 2 and aliquid esterified propoxylated glycerin from Example 1.

[0272] In the case of Mixture A, solid and liquid components are mixedat a proportion of 6 weight parts of the solid component to 94 weightparts of the liquid component, and agitated to a molten liquid state ata temperature of 68° C. in a temperature controlled agitated vessel. Inthe case of Mixtures B & C solid and liquid components are mixed at aproportion of 10 weight parts of the solid component to 90 weight partsof the liquid component, and agitated to a molten liquid state at atemperature of 68° C. in a temperature controlled agitated vessel. Ineach case, the molten mixture is then pumped at a flow rate of 280pounds per hour (127.3 kg/hr.) through two serially-arrangedbrine-jacketed (−1.0° C. brine coolant) Cherry Burrell Votator Model3SSHE scrapped wall heat exchangers, operating at 1690 RPM. Thetemperature of the mixture is lowered from 68° C. to 21° C. within aresidence time of 20 seconds. Upon exiting the Cherry Burrell heatexchangers, the solid sucrose polyester portion is substantiallycrystallized and forms small (<10 micron) discrete and unaggregatedcrystal particles. The substantially crystallized composition is thenpassed through a heat exchanger which adjusts the temperature (asneeded) to 21° C., and into a jacketed scraped wall tank where it isheld under continued shearing for two hour at 21° C. The batch temperingtank is 12 inches in diameter and 28 inches deep, holds 100 pounds (45.5kg) of the composition, and is equipped with an anchortype agitatorwhich turns at 14 rpm; there are no dead spots in the material in thevessel. In each case, the heat exchanger outlet and continued shearinghold temperature is 21° C.

[0273] The resulting flowable nondigestible oil compositions (A, B andC) have the following physical attributes:

[0274] The liquid component has a complete melt point less than 37° C.

[0275] The solid component has a complete melt point which is greaterthan 37° C.

[0276] Substantially all of the solid component is in the form ofcrystallized particles.

[0277] The flowable composition has a Consistency in a temperature rangeof 20-40 degrees Centigrade of less than about 600 P.sec^((n−1)). TABLEA Fatty Acid Composition and Ester Distribution of the Solid SucrosePolyester and the Liquid Sucrose Polyester Components of Olean ®, andthe Solid Esterified Linked Propoxylated Glycerin and the LiquidEsterified Propoxylated Glycerin Solid Liquid Solid Esterified LiquidSucrose Sucrose Linked Esterified Polyester Polyester PropoxylatedPropoxylated (weight %) (weight %) Glycerin Glycerin Fatty AcidComponent C8 — — — — C10 — — — — C12 0 — — — C14 0 — — — C16 1.2 9.7 —9.5 C17 0 0.1 — 0.1 C18 4.6 5.9 — 7.5 C18:1 3.7 64.5 — 58.4 C18:2 10.918.9 — 22.2 C18:3 0 0.2 — 1.0 C20 4.6 0.3 0.1 0.3 C22 71.7 0.2 99.8  0.4C22:1 0.2 — — — C24 2.8 — 0.1 — Other 0.4 0.2 0.6 Ester % %Distribution. Octa 71.6 78.7 Hepta 28.1 21.0 Hexa 0.2 0.2 Penta 0.1 0.2Tetra * * Tri Not 93.8% Characterized. Di 6.0% Mono 0.2%

What is claimed is:
 1. A flowable nondigestible oil compositioncomprising, preferably 50-99% by weight, a liquid component having acomplete melt point less than 37° C.; and, preferably 1-50% by weight, asolid component having a complete melt point of at least about 37° C.;wherein the solid component is in the form of crystallized particles;wherein at least one of the liquid component and the solid componentcomprises a material selected from esterified linked alkoxylatedpolyols; esterified epoxide-extended polyols; and mixtures thereof,preferably wherein the liquid component comprises a material selectedfrom esterified linked alkoxylated polyols; esterified epoxide-extendedpolyols; and mixtures thereof; and wherein the flowable nondigestiblecomposition has a Consistency in a temperature range of 20-40° C. ofless than about 600 P.sec^((n−1)), preferably less than about 400P.sec^((n−1)), more preferably less than about 200 P.sec^((n−1)), mostpreferably less than about 100 P.sec^((n−1)).
 2. The composition ofclaim 1 wherein the solid component comprises a material selected fromthe group consisting of (i) a solid saturated polyol polyester, (ii) asolid diversely esterified polyol polyester, (iii) a polyol polyesterpolymer, and (iv) combinations thereof; most preferably wherein thesolid saturated polyol polyester and the solid diversely esterifiedpolyol polyester are in the form of cocrystallized particles.
 3. Theflowable nondigestible oil composition according to any of the aboveclaims wherein the crystallized particles have a maximum dimension offrom about 1 micron to about 30 microns, preferably from 2 microns to 5microns.
 4. The flowable nondigestible oil composition according to anyof the above claims wherein solid saturated polyol polyester is selectedfrom hepta-substituted saturated fatty acid polyol polyester,octa-substituted saturated fatty acid polyol polyester, and mixturesthereof, having C20-C24 saturated fatty acid radicals, preferablywherein the solid saturated polyol polyester comprises octabehenatesucrose polyester, and wherein the solid diversely esterified polyolpolyester comprises octasaturated sucrose polyester; preferably whereinthe esters are selected from behenate and a mixture of C18:1 and C18:2unsaturate; more preferably, wherein the solid polyol fatty acidpolyester has fatty acid esters comprising long chain saturated fattyacid esters and long chain unsaturated fatty acid esters in a ratiothereof of 5:3 to 7:1, preferably from 6:2 to 6.5:1.5; and wherein thesolid diversely esterified polyol polyester is selected fromhepta-substituted diversely esterified polyol polyester,octa-substituted diversely esterified polyol polyester, and mixturesthereof, having fatty acid radicals comprising a) long chain saturatedfatty acid radicals, and b) dissimilar fatty acid radicals which aredissimilar from the long chain saturated fatty acid radicals and areselected from the group consisting of i) long chain unsaturated fattyacid radicals, ii) short chain saturated fatty acid radicals, and iii)mixtures thereof; most preferably, wherein the solid saturated polyolpolyester is a sucrose polyester comprising at least 5% by weightsucrose octabehenate, and preferably the solid sucrose polyester has acomplete melt point of at least about 60° C.
 5. A process for making aflowable nondigestible oil composition comprising a liquid componenthaving a complete melt point less than 37° C., and a solid componenthaving a complete melt point of at least about 37° C., the processcomprising the steps of: a) providing a mixture comprising the liquidcomponent and the solid component, wherein at least one of the liquidcomponent and the solid component comprises a material selected fromesterified linked alkoxylated polyols; esterified epoxide-extendedpolyols; and mixtures thereof, b) melting the nondigestible oilcomprising the solid component and the liquid component, c)crystallizing at least a substantial portion of the solid component,preferably wherein said crystallization is accompanied by i) reducingthe temperature of the melted nondigestible oil to a crystallizationtemperature less than the onset crystallization temperature of the solidcomponent; ii) holding the nondigestible oil at the crystallizationtemperature for a time sufficient to crystallize at least a substantialportion of the solid component; and more preferably wherein thecrystallizing step further comprises continued holding the crystallizedcomposition at a crystallization temperature whereby the crystallizationof the solid component is substantially complete; and d) shearing thenondigestible oil composition during the step of crystallizing, therebyforming the solid component into crystallized particles, preferablywherein the shearing further comprises continued shearing of thecomposition during the continued holding step; wherein the flowablenondigestible oil has a Consistency in a temperature range of 20° to 40°C. of less than about 600 P.sec^((n−1)), preferably wherein the step ofcrystallizing and step of shearing are both conducted in a scraped wallheat exchanger or equivalent.
 6. The process according to claim 5wherein the crystallization temperature is about 5° C. or more below theonset crystallization temperatures of the solid component.
 7. Theprocess according to any of claims 5 or 6 wherein the flowablenondigestible oil composition has a Consistency in a temperature rangeof 20°-40° C. of less than 400 P.sec^((n−1)), preferably less than 200P.sec^((n−1)); more preferably less than 100 P.sec^((n−1)).
 8. Theprocess according to any of claims 5-7 wherein the solid component has acomplete melt point of at least 60° C.
 9. The process according to anyof claims 5-8 wherein in at least 80%, preferably at least 95%, of thesolid component is crystallized, preferably wherein the solid componentis crystillized at a crystallizing temperature of at least about 10° C.below the onset crystallization temperature of the solid component, morepreferably wherein crystallizing comprises cooling the composition fromthe molten temperature to the crystallization temperature at a coolingrate of about 100-300° C./min., most preferably wherein crystallizing iscompleted within about 30 seconds.
 10. The process according to any ofclaims 5-9 wherein the step of shearing comprises shearing thecrystallizing composition at a shear rate of about 400 sec⁻¹ to about8000 sec⁻¹, preferably wherein a diluting amount of the liquid componentis added to the crystallized composition in a ratio of from about 0.5:1to about 0.1:1; most preferably further comprising the step of adding astabilizing amount of a diluent liquid after the step of crystallizingthe solid polyol fatty acid polyester.
 11. The process according to anyof claims 5-10 further comprising the step of tempering the flowablenondigestible oil composition by reducing the temperature of thecomposition to a tempering temperature which is below an intendedstorage temperature, and preferably shearing the tempered composition.